JP3261777B2 - Chlorosulfonated polyolefin resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chlorosulfonated polyolefin resin composition having excellent workability and suitably used for automobile hoses, gas hoses, sealing materials, roofing materials and the like.

[0002]

2. Description of the Related Art Conventionally, chlorosulfonated polyolefins have excellent weather resistance, chemical resistance, flame resistance, and mechanical properties, and are utilized in automotive hoses, gas hoses, sealing materials, roofing materials, etc. by utilizing these characteristics. Have been. When used as a crosslinked rubber, it is filled with carbon black, calcium carbonate, magnesium silicate, aluminum silicate and the like in order to improve mechanical properties.

[0003]

However, when the above fillers and the like are compounded and molded, there is a problem that the dispersibility and adhesion during kneading and the appearance of the molded product are not good. In view of the above, an object of the present invention is to provide a chlorosulfonated polyolefin-based resin composition having excellent moldability and good appearance of a molded article.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have achieved the above object by blending a clay treated with a specific amount of chlorinated polyethylene and a specific silane coupling agent. This led to the completion of the present invention based on this finding. That is, the present invention relates to (A) chlorosulfonated polyolefin 50 to 9
0 parts by weight, (B) 50 to 10 parts by weight of chlorinated polyethylene [(A) + (B) = 100 parts by weight], (C) an average particle diameter of 0.1 to 1.0 μm, and a mercapto silane 20 to 150 parts by weight of clay treated with a coupling agent,
The present invention provides a chlorosulfonated polyolefin-based resin composition comprising (D) 0.5 to 20 parts by weight of an organic peroxide and (E) 0.1 to 10 parts by weight of a polyfunctional compound. Hereinafter, the present invention will be described specifically.

(A) Chlorosulfonated polyolefin The chlorosulfonated polyolefin (hereinafter referred to as CSM) used in the present invention is produced by dissolving a polyolefin powder or particles described below in an organic solvent and chlorosulfonating. Can be. As a method of chlorosulfonation, chlorine and sulfurous acid gas (for example,
No. 838) and a method of blowing chlorine and sulfuryl chloride alone (for example, Japanese Patent Publication No. 39-12113) into a solution is known, and CSM is industrially produced and used in various fields.

The polyolefin in the present invention is a homopolymer or copolymer of an α-olefin, for example, a medium-low pressure polyethylene, a high pressure polyethylene, a linear low density polyethylene, a polypropylene, a polybutene, an ethylene-propylene copolymer, Examples thereof include an ethylene-butene-1 copolymer and an ethylene-vinyl acetate copolymer. Among them, various polyethylenes and ethylene-propylene copolymers are preferred.

(B) Chlorinated polyethylene Further, the chlorinated polyethylene used in the present invention (hereinafter referred to as C
PE) is obtained by chlorinating polyethylene powder or particles in an aqueous suspension or by chlorinating polyethylene dissolved in an organic solvent, and preferably obtained by the former method. The chlorine content of the CPE is usually 20 to 50% by weight, particularly 25% by weight.
~ 45% by weight is preferred. If the chlorine content is less than 20% by weight, the amount of remaining crystals is large, and a flexible rubber cannot be obtained.
If it exceeds 50% by weight, rubber elasticity becomes poor. Amorphous chlorinated polyethylene having no residual crystals is preferred because it has better flexibility and may be crystalline.

The polyethylene is obtained by homopolymerizing ethylene or copolymerizing ethylene with at most 10% by weight of an α-olefin (generally, at most 12 carbon atoms). Its density is usually from 0.91 to 0.97 g / cm ³ . The molecular weight is usually 50,000 to 700,000.

(C) Clay The clay used in the present invention is a kaolin-based clay mainly composed of naturally occurring hydrous aluminum silicate. The average particle size of the clay is 0.1 to 1.0 μm. If the average particle size is less than 0.1 μm, the effect of improving the tensile strength is poor. On the other hand, if it exceeds 1.0 μm, the effect of improving the tensile strength is inferior, and the extrudability is lowered, which is not preferable.

[0010] The clay must be surface-treated with a mercapto silane coupling agent. The silane coupling agent is an organic silane compound used for surface treatment for the purpose of improving the adhesiveness between the resin and a resin filler such as glass fiber. Among them, mercapto compounds are particularly excellent, and other coupling agents such as vinyl compounds and amino compounds are inferior in tensile strength and weather resistance. The mercapto-based silane coupling agent has the general formula R ₁ —Si (OR
₂ ) _{3 wherein} R ₁ represents a mercaptoalkyl group and R ₂ represents an alkyl group. Examples thereof include γ-mercaptopropyltrimethoxysilane, γ-mercaptomethyltrimethoxysilane, and γ-mercaptomethyltrimethoxysilane.
And mercaptoethyltrimethoxysilane. The surface treatment of clay is described, for example, in JP-B-41-170.
No. 49, Japanese Patent Publication No. 60-6739 and the like can be carried out by known methods.

(D) Organic peroxide The organic peroxide used in the present invention is not particularly limited, but those having a decomposition temperature (temperature at which the half-life is 1 minute) of 120 ° C. or more are particularly preferred. Desirably, those having a temperature of 140 ° C. or higher are particularly preferable. Representative examples of suitable organic peroxides include 1,1-bis-tertiary-butylperoxy-
Ketone peroxides such as 3,3,5-trimethylcyclohexane, hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide,
Peroxyesters such as 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, diacyl peroxides such as benzoyl peroxide and dialkyl peroxides such as dicumyl peroxide, furthermore tertiary Percarbonates such as -butyl-oxyisopropyl carbonate.

(E) Polyfunctional compound The polyfunctional compound used in the present invention is a compound having at least two reactive double bonds in one molecule. Examples of the compound include a compound having a diallyl group or a triallyl group, which is used as a crosslinking aid in a general rubber field. Specific examples include triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalic acid, triallylamine, diallyl maleic acid and the like.

(F) Composition Ratio The composition ratio of CSM in the total amount of CSM and CPE is 50 to 90% by weight, preferably 60 to 80% by weight, and more preferably 65 to 75% by weight. CSM
If the composition ratio is less than 50% by weight, the processability and the mechanical properties decrease. On the other hand, if it exceeds 90% by weight, the dispersibility and adhesion during kneading deteriorate.

The mixing ratio of other components to the total amount of 100 parts by weight of CSM and CPE is as follows. The compounding ratio of the clay is 20 to 150 parts by weight, preferably 50 to 150 parts by weight, and more preferably 70 to 13 parts by weight.
0 parts by weight. If the compounding ratio of the clay is less than 20 parts by weight, the effect of improving the properties is poor. On the other hand, extrudability exceeding 150 parts by weight and mechanical properties are undesirably reduced.

The compounding ratio of the organic peroxide is 0.5 to
20 parts by weight, preferably 1.0 to 15 parts by weight, and particularly preferably 2.0 to 10 parts by weight. When the compounding ratio of the organic peroxide is less than 0.5 part by weight, the property improvement after crosslinking is not sufficient. On the other hand, even if it exceeds 20 parts by weight, the characteristics are not further improved. The compounding ratio of the polyfunctional compound is 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, and particularly preferably 1 to 5 parts by weight. If the compounding ratio of the polyfunctional compound is less than 0.1 part by weight, the properties after crosslinking are not sufficiently improved. On the other hand, even if it exceeds 10 parts by weight, the characteristics are not further improved.

In addition to the above components, vulcanization accelerators such as thiourea-based accelerators and thiuram-based accelerators used in the general rubber industry may be blended. Although the composition of the present invention can be obtained by uniformly mixing the above substances, various additives generally used in the rubber and resin industries, for example, a plasticizer, a lubricant,
Antioxidants, ultraviolet absorbers, flame retardants, antistatic agents, various fillers, and the like can be added according to the purpose of use.

(G) Mixing Method When manufacturing the composition of the present invention, the method of mixing the compound is performed by using a mixer such as an open roll, a kneader or a Banbury mixer generally used in the technical field. And knead it. The composition of the present invention is an extruder usually used in the general rubber industry,
It may be formed into a desired shape using a molding machine such as an injection molding machine, a compression molding machine and a calender molding machine. Also,
A method of manufacturing a molded product while crosslinking (vulcanizing), that is, a method of simultaneously proceeding vulcanization and molding can be applied to form a desired shape.

[0018]

The present invention will be described in more detail with reference to the following examples. The extrudability was measured by attaching a 2-inch Garvey die to the end of a rubber extruder and setting the cylinder temperature to 60 ° C.
Extrusion molding was performed at a die temperature of 60 ° C., a head temperature of 70 ° C., and a screw rotation speed of 30 rpm. The appearance of the obtained molded product was visually shown in the following four stages. ◎ Very good ○ Good △ Somewhat bad × Bad

The amounts of resin adhering to the screw, die, and head of the extruder are visually shown in the following four stages. ◎ almost none ○ a little △ quite a lot × many

The crosslinkability is measured by using an oscillating disc rheometer to determine the minimum torque (hereinafter referred to as M
L) and optimal crosslinking time (hereinafter referred to as T90)
Was measured. The compression set was measured after standing for 22 hours in an oven set at 100 ° C. according to JIS K6301. The tensile test is performed according to JIS K6301 according to JI
Using's S3 dumbbell Shopa type tester used to tensile strength (hereinafter, T _B hereinafter) and elongation (hereinafter, referred to as E _B) were measured. The heat resistance test was carried out in a gear oven set at a temperature of 120 ° C according to JIS K6301.
Subjected to tensile tests after standing 0 hours to determine the rate of change of T _B and E _B.

Further, the used CSM, CPE, clay,
The types and physical properties of the silane coupling agent, the organic peroxide and the polyfunctional compound are shown below. As CSM, chlorine content 35 wt%, specific gravity of 1.18 and a Mooney viscosity _{(ML 1 + 4, 100 ℃} ) is Showa Denko de is 55
Hypalon 40 (trade name, manufactured by UPON CORPORATION) was used. CP
E is a noncrystalline CPE having a chlorine content of 40% by weight.
Eraslen 401A manufactured by Showa Denko KK was used. As clay, J.I. M. Huber LG
B (hard clay) was used. As silane coupling agents, γ-mercaptopropyltrimethoxysilane (hereinafter, referred to as MS-1), γ-mercaptomethyltrimethoxysilane (hereinafter, referred to as MS-2) and γ-mercaptoethyltrimethoxysilane (hereinafter, MS-3) Was used. For comparison, γ-aminopropyltriethoxysilane (hereinafter, referred to as AS) and γ-methacryloxypropyltriethoxysilane (hereinafter, referred to as VS) were used. Ketone peroxide 2,5-dimethylhexane-2,5-dihydroperoxy (hereinafter referred to as PO) was used as an organic peroxide, and triallyl isocyanurate (hereinafter referred to as TAIC) was used as a polyfunctional compound. .

Examples 1 to 5 and Comparative Examples 1 to 9 CSM, CPE, clay, whose types and quantities are shown in Table 1
PO and TAIC and 20 parts by weight of trimellitic acid ester as a plasticizer were blended. The mixing method is P
The mixture excluding O and TAIC was charged into a kneader mixer and kneaded under pressure for 20 minutes. Next, the kneaded material was wound around an open roll, PO and TAIC were kneaded, and then formed into a predetermined sheet. The obtained sheet was extruded, and the extrudability and the amount of resin adhered inside the extruder were each visually confirmed.

The crosslinkability was set at a temperature of 180 ° C., a maximum torque of 100 kg-cm, and a rotor angle of 3 °, and ML and T90 were measured. Compression set is 200kg / pressure
Crosslinking was performed for 20 minutes under the conditions of cm ² and a temperature of 180 ° C., and the compression set of the obtained crosslinked product was measured. Further, the sample to be subjected to the tensile test and the heat resistance test has a sheet thickness of 2 m.
m, 15cm each in a vertical and horizontal molding die, pressure 20
Crosslinking was carried out at 0 kg / cm ^{2 at} a temperature of 180 ° C. for 10 minutes. The obtained crosslinked product was subjected to a tensile test and a heat resistance test. Table 2 shows the above results.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

The resin composition of the present invention has the following features. (1) The compound has good kneading properties. (2) Good extrudability. (3) The resin adhesion amount inside the extruder is small. (4) Excellent mechanical properties (particularly, tensile strength and heat resistance). Such as wire covering materials, industrial parts, automobile parts,
It can be used in various fields such as building materials. Typical examples of the application include an electric wire sheath material and a hose.

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 23/28 C08L 23/34

Claims (1)

(57) [Claims] (A) 50 to 90 parts by weight of a chlorosulfonated polyolefin, (B) 50 to 1 parts of a chlorinated polyethylene.
0 parts by weight [(A) + (B) = 100 parts by weight], (C) 20 to 150 parts by weight of clay having an average particle diameter of 0.1 to 1.0 μm and treated with a mercapto silane coupling agent, A chlorosulfonated polyolefin resin composition comprising (D) 0.5 to 20 parts by weight of an organic peroxide and (E) 0.1 to 10 parts by weight of a polyfunctional compound.