JPH08176375A - Chlorinated polyolefinic rubber composition - Google Patents

Abstract

PURPOSE: To obtain a recyclable chlorinated polyolefinic rubber composition having excellent mechanical strengths, flexibility and calendering and proper magnetic properties, by blending a chlorinated polyolefin with specific magnetic powder and an epoxy compound. CONSTITUTION: This composition comprises (A) 100 pts.wt. of a chlorinated polyolefin (preferably a chlorinated polyethylene or a chlorinated ethylene- propylene copolymer), (B) 100-600 pts.wt. of a mercapto-based silane coupling agent (e.g. γ-mercaptopropyltrimethoxysilane), (C) 1-10 pts.wt. of an epoxy compound (preferably an epoxidized vegetable oil) and (D) 0.1-10 pts.wt. of a high molecular-weight hindered phenol compound (preferably a bis[2-methyl-4- 3-n- alkylthiopropionyloxy}-5-t-butylphenyl] sulfide) wherein an n-alkyl is 12-14C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a recyclable chlorinated polyolefin rubber composition having excellent flexibility and calendar processability, good mechanical strength, and proper magnetic properties, and a doormat using the same. Regarding

[0002]

2. Description of the Related Art An entrance mat is a mat that is laid at the entrance of a building and wipes off the dirt on the soles of people who come and go. The mat is composed of a surface base cloth and a rubber plate, and there are an integral type in which these are integrally fixed and a separable type. While the former integrated type has the advantage of being thin and lightweight, it has the disadvantages such as difficulty in cleaning the base cloth and high replacement cost, and the latter separate type is being developed.

[0003]

However, since the separate type requires a one-touch connection between the base cloth and the rubber plate, it is difficult to make it thin and it may interfere with the opening and closing of the door. Their applications were often limited.
The present invention has been made in view of such circumstances, and an object of the present invention is to provide a rubber sheet for an entrance mat, which is a separate type and can be thin as in the integrated type.

[0004]

As a result of intensive studies, the present inventors have found that the above object can be achieved by blending a specific magnetic powder and an epoxy compound with a chlorinated polyolefin. The present invention has been completed based on the above. That is, the present invention relates to (A) 100 parts by weight of chlorinated polyolefin and (B) magnetic powder treated with a mercapto-based silane coupling agent.
A chlorinated polyolefin rubber composition comprising 0 to 600 parts by weight, (C) an epoxy compound 1 to 10 parts by weight, and (D) a high molecular weight hindered phenol compound 0.1 to 10 parts by weight. Hereinafter, the present invention will be specifically described.

The chlorinated polyolefin (A) in the present invention (hereinafter referred to as "CPO") is obtained by suspending a polyolefin powder in water or by chlorinating a solution of the polyolefin powder in an appropriate organic solvent. The production method is a known technique, and in the present invention, the method obtained by the former method is preferable. The polyolefin is a homopolymer of ethylene or a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms. The copolymerization ratio of α-olefin is generally 40% by weight or less. Specific examples of the polyolefin include polyethylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer and the like.

Specific examples of CPO include chlorinated polyethylene, chlorinated ethylene-propylene copolymer, chlorinated ethylene-propylene-non-conjugated diene copolymer and the like. Among these, chlorinated polyethylene and chlorinated ethylene-propylene copolymer are preferable. The chlorine content of the CPO of the present invention is generally 20 to 50% by weight.
And particularly preferably 25 to 45% by weight. The CPO of the present invention may be blended with another type of compatible rubber component. Examples of the rubber component include chlorosulfonated polyethylene, butyl rubber, ethylene-vinyl acetate and the like. The compounding amount of these rubber components is CPO.
It is at most 100 parts by weight per 100 parts by weight.

The (B) magnetic powder in the present invention is
The powder is generally called ferrite, and examples thereof include barium ferrite, strontium ferrite, lead ferrite, and calcium ferrite. Of these, barium ferrite and strontium ferrite are preferable. The particle size of the magnetic powder is preferably 0.5 to 2 μm, and particularly preferably 0.8 to 1.5 μm.

The magnetic powder of the present invention must be treated with a mercapto type silane coupling agent. The coupling agent has the general formula: R ₁ —Si (OR ₂ ) ₃ (where R
₁ is a mercaptoalkyl group, and R ₂ is an alkyl group). As a specific example,
For example, γ-mercaptopropyltrimethoxysilane, γ
-Mercaptomethyltrimethoxysilane, γ-mercaptoethyltrimethoxysilane and the like can be mentioned. For the silane treatment method, Japanese Patent Publication No. 41-17049, Japanese Patent Publication No.
It can be carried out by the conventionally known means described in JP-A-60-6379. The amount of the magnetic powder blended is 100 to 600 parts by weight based on 100 parts by weight of the component (A).
50 parts by weight is preferable, and 200 to 500 parts by weight is particularly preferable. If the blending amount of the magnetic powder is less than 100 parts by weight, the magnetic force is poor. On the other hand, if it exceeds 600 parts by weight, flexibility and workability are deteriorated, which is not preferable.

The epoxy compound (C) in the present invention is generally used as a lubricant and stabilizer in the resin field. Specific examples of the epoxy compound include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, adipic acid diglycidyl ester, trimethylolpropane polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether. , Butanediol diglycidyl ether, epoxidized soybean oil, epoxidized olive oil, epoxidized safflower oil, epoxidized corn oil, epoxidized linseed oil, epoxidized animal oils, epoxidized liquid rubber, epoxidized polybutene, epoxidized polyisobutylene , Epoxidized terpene resin, epoxidized silicone resin, hydrogenated bisphenol A diglycidyl ether, phenol novolac polyglycidyl ether, 4,4'- Examples thereof include diglycidyloxy-3,3 ′, 5,5′-tetramethylbiphenyl, bis (4-glycidylaminophenyl) methane, and triglycidyl isocyanurate. Among these, epoxidized vegetable oils are particularly preferable. These are epoxidized unsaturated double bonds of natural vegetable oils using, for example, peracid, and commercially available products such as Asahi Denka Kogyo Co., Ltd.
O-130P (epoxidized soybean oil), O-180A
(Epoxidized linseed oil), etc.

The compounding amount of the epoxy compound with respect to 100 parts by weight of the component (A) is 1 to 10 parts by weight, preferably 2 to 9 parts by weight, and particularly preferably 3 to 7 parts by weight. If the blending amount of the epoxy compound is less than 1 part by weight, the thermal stability will decrease. On the other hand, if it exceeds 10 parts by weight, bleeding on the surface of the molded product becomes a problem.

The high molecular weight hindered phenol compound (D) in the present invention is called a high molecular weight type among phenolic antioxidants, and among them, a sulfide type containing sulfur is preferable. In particular, bis [2-methyl-4- {3-n-alkylthiopropionyloxy} -5-t-butylphenyl] which is liquid at room temperature
Sulfide (however, n-alkyl has 12 to 1 carbon atoms)
4) is preferred. The compounding amount of the phenol compound with respect to 100 parts by weight of the component (A) is 0.1 to 10 parts by weight,
0.5 to 8 parts by weight is preferable, and 1 to 5 parts by weight is particularly preferable. If the blending amount of the epoxy compound is less than 0.1 part by weight, the heat resistance will decrease. On the other hand, even if it exceeds 10 parts by weight, the characteristics are not further improved.

Further, if desired, conventional additives such as a plasticizer, a lubricant, a heat stabilizer, an antiblocking agent, an antistatic agent, a release agent, a pigment and a filler are added to the composition of the present invention. May be. The composition of the present invention can be obtained by mixing using a conventionally known mixing method, for example, a Henschel mixer, a ribbon mixer, and the like, and further performing melt mixing using an open roll, a kneader, a Banbury mixer, an extruder, and the like. The obtained composition is a film, a sheet, or a sheet prepared by a known melt molding method or compression molding method.
It can be molded into a tube, a container or the like for use.

The sheet obtained by molding the composition of the present invention is particularly suitable as a rubber sheet for an entrance mat. By mixing the magnetic powder in the surface cloth sheet,
It does not shift during use, can maintain appropriate adhesiveness, and can be easily peeled off. Further, by using magnetic force as the bonding method, it is possible to achieve the same thinness as the integrated type.

[0014]

The present invention will be described in more detail with reference to the following examples. The physical property evaluation was based on the following methods. (1) Calendar Workability The situation when a sheet having a thickness of 1 mm was prepared under the conditions of a roll surface temperature of 80 ° C. and a fabric temperature of 50 ° C. was evaluated using the 8-inch reverse L-type calendar tester in the following three stages. ○ ・ ・ ・ ・ Roll wrapping property and good surface skin △ ・ ・ ・ ・ Surface skin is good, but some air bubbles are entrapped × ・ ・ ・ ・ The bite is bad and there is a recess on the surface (2) Tensile test In accordance with JIS K6301 Then, the tensile strength (hereinafter referred to as "T
_B "hereinafter), was measured growth rate (hereinafter referred to as" that E _B ") permanent elongation (hereinafter referred to as" ΔL "). (3) Heat resistance test J was placed in a JIS gear oven set to 120 ° C.
After leaving IS3 dumbbells for 120 hours, proceed to (2) above
The tensile test was carried out by the method described above to determine the retention rates (%) of T _B and E _B. (4) Weather resistance test After performing an exposure test for 2000 hours at a temperature of 63 ° C. using a sunshine weatherometer, the above (2)
The tensile test was carried out by the method described above to determine the retention rates (%) of T _B and E _B. (5) Compression set According to JIS K6301, measurement was performed after standing for 22 hours in an oven set at a temperature of 70 ° C. (6) Magnetic force A Gauss meter was used for a sheet magnetized with a pole plate (dimension: 200 mm x 200 mm, magnetizing yoke; 50 poles, 3 mm pitch) using a condenser type magnetizer (Japan Electromagnetic Sector SCB-30). The magnetic force was measured.

The component (A) has a chlorine content of 30.
% Of non-crystalline chlorinated polyethylene as a component (B), barium ferrite having an average particle size of 1 μm (hereinafter referred to as “Ba-F”) and strontium ferrite having an average particle size of 1 μm (hereinafter “St- "F") was used. Γ-mercaptopropyltrimethoxysilane (hereinafter referred to as “silane 1”), γ-mercaptomethyltrimethoxysilane (hereinafter referred to as “silane 2”) and γ
-Mercaptoethyltrimethoxysilane (hereinafter referred to as "silane 3") was used. Further, γ-aminopropyltrimethoxysilane (hereinafter referred to as “aminosilane”) was used for comparison. Epoxidized soybean oil as the component (C) and bis [2-methyl-4- {3-n as the component (D).
-Alkylthiopropionyloxy} -5-t-butylphenyl] sulfide (however, n-alkyl has 12 carbon atoms) was used.

Examples 1 to 8 and Comparative Examples 1 to 8 Each component whose type and blending amount are shown in Table 1 was put into a kneader, and after kneading under pressure for 15 minutes, calendering workability was evaluated. Further, the composition was wound on an open roll to form a predetermined sheet. The tensile test, heat resistance test, weather resistance test, and magnetic force of each sheet were measured. Table 2 shows the above results.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

INDUSTRIAL APPLICABILITY The resin composition of the present invention is excellent in flexibility and calendering workability, has good mechanical strength, has appropriate magnetic properties, and is recyclable. Is useful as

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C08K 5/15 KET 5/36 KFD 9/06

Claims (6)

[Claims] 1. (A) 100 parts by weight of chlorinated polyolefin, (B) 100 to 600 parts by weight of magnetic powder treated with a mercapto-based silane coupling agent, (C) 1 to 10 parts by weight of epoxy compound and (D). High molecular weight hindered phenol compound A chlorinated polyolefin rubber composition comprising 0.1 to 10 parts by weight. 2. The chlorinated polyolefin rubber composition according to claim 1, wherein the magnetic powder (B) is barium ferrite or strontium ferrite and has an average particle size of 0.5 to 2 μm. 3. The chlorinated polyolefin rubber composition according to claim 1 or 2, wherein the epoxy compound (C) is epoxidized soybean oil. 4. The high molecular weight hindered phenol compound (D) is bis [2-methyl-4- {3-n-alkylthiopropionyloxy} -5-t-butylphenyl] sulfide (provided that the carbon of n-alkyl is Number is 12 to 1
4) The chlorinated polyolefin rubber composition according to any one of claims 1 to 3. 5. A rubber sheet formed by molding the chlorinated polyolefin-based rubber composition according to any one of claims 1 to 4. 6. An entrance mat comprising the rubber sheet according to claim 5 and a surface base cloth sheet.