JPS59140248A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent flame retardance, processability, mechanical strength and resistance to permanent set on compression and tension, consisting of a vinyl chloride resin, a specified chloroprene polymer and a plasticizer. CONSTITUTION:5-200pts.wt. chloroprene polymer contg. 40-100wt% toluene- insoluble gel component and 20-150pts.wt. plasticizer such as di-2-ethylhexyl phthalate are blended with 100pts.wt. vinyl chloride resin. USE:Hose, gasket, film, wire coating material, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl chloride resin composition that has excellent resistance to permanent deformation under compression and tension, flame retardancy, and good processability and mechanical strength.

Conventionally, soft vinyl chloride resins containing plasticizers have been widely used as materials for hoses, gaskets, leather, films, wire coatings, and the like.

However, this soft vinyl chloride resin has the disadvantage that its shape retention at high temperatures and permanent deformation resistance are significantly inferior to that of vulcanized rubber. As an improvement method, for example, the average degree of polymerization is 25
When using a high polymerization degree vinyl chloride resin of 00 to 4000, compression set (J engineering 5x-6301, 70℃ x 22
Hr) kl, 60-7 of conventional soft vinyl chloride resin
Although it is reduced to a factor of nearly 50 compared to 0%, it is unsuitable as a material for hoses, gaskets, etc. that require even lower permanent deformation characteristics. Therefore, the average degree of polymerization is further increased from 4.000 to io, o o o, or 1.
Even if a vinyl chloride resin of 0.000 or more is used, not only the expected low permanent set cannot be obtained, but also the productivity during production of the vinyl chloride resin is low, and the molding performance is also deteriorated, so it is not preferable. do not have.

Furthermore, as described in JP-A-57-187341, acrylonitrile containing del, which is insoluble in methyl ethyl ketone,
When the IJ sil-tagene copolymer is blended with a vinyl chloride resin together with a plasticizer, it also has the disadvantage that the flame retardance, which is a characteristic of the vinyl chloride resin, deteriorates. Furthermore, regarding the composite of vinyl chloride resin and chloroprene polymer, it has been reported that chloroprene polymer lacks compatibilism with vinyl chloride resin compared to acrylonitrile-citadiene copolymer, and Sulfur-based polymers do not improve the physical properties of chloroprene polymers, such as oil resistance, heat resistance, and creep resistance.Also, when used as a polymer plasticizer for vinyl chloride resin, the properties of acrylonitrilutazoene copolymer The drawback was that no system could be found that exhibited unique physical properties (e.g., oil resistance, abrasion resistance, bending strength, etc.) comparable to that of conventional methods.

In order to improve the above-mentioned drawbacks, the present inventors have made intensive studies and found that the gel content insoluble in toluene is 40 to 100% by weight.
A vinyl chloride resin composition containing chloroprene polymer, vinyl chloride resin, and a plasticizer as main components can be compressed and It was discovered that the permanent set resistance due to tension was significantly improved, and the present invention was achieved. That is, in the present invention, a chloroprene polymer, which has hardly been practically used in combination with a vinyl chloride resin, is modified to contain 40 to 100% by weight of a toluene-insoluble R content, and the chloroprene polymer is By combining 5 to 200 parts by weight of a polymer, 100 parts by weight of a vinyl chloride resin, and a plasticizer as main components, permanent deformation due to compression and tension, which was a drawback of conventional soft vinyl chloride resin compositions, is significantly reduced. The present invention is also characterized by providing a novel thermoplastic vinyl chloride resin composition that has highly improved flame retardancy, processability, and mechanical properties.

The chloroprene polymer used in the present invention is characterized by containing 40 to 100% by weight of del content insoluble in toluene, and its structural unit is a polymer whose main component is chloroprene. There are no limitations on the method of blending the gel or sol components. That is, as a method for producing gel, (11 chlororune,
Alternatively, a mixture of chloroprene and a small amount of one or more copolymerizable monomers can be used in an amount of 40 to 100% by weight.
(2) A method of polymerizing chloroprene or a mixture containing a small amount of one or more monomers copolymerizable with chloroprene, such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, etc. A method obtained by polymerization in the presence of a polyfunctional crosslinking agent such as ethylene glycol dimethacrylate or trimerolpropane trimethacrylate (for example, described in Jibun No. 47-65775), or (3) a method in which the toluene soluble sol content is 40 wt. Any production method may be employed, such as a method in which a chloroprene polymer of less than 100% is subjected to a post-crosslinking reaction using a crosslinking agent or by irradiation with radiation.

In addition, the monomers (1) and (2) copolymerizable with chloroprene are 2. Ro-dimethyl-1,5-butadiene, 2
．． 5-dichloro-1,6-butadiene/, butadiene/, diene compounds such as isoprene, ether pickles such as methyl vinyl ether, vinyl esters such as vinegar and beer, ketones such as methyl vinyl ketone, methyl acrylate, means esters of acrylic acid and methacrylic acid such as methyl methacrylate, amides such as methacrylamide and acrylonitrile, and di-IJ sils;
The chloroprene polymer (3) also contains the same copolymer as above.

In the present invention, the weight of the toluene-insoluble roroprene polymer is 1 liter, and the chloroglene polymer is 1.9 (Wl:),
Add toluene 100- and leave it at room temperature for 72 hours, dry and weigh [W2] F paper (,rIs P-6801
, 5 types), washed several times with fresh toluene, and
The paper and del content were air-dried and weighed [W3], and the weight was calculated using the following formula.

If the gel content of the above-mentioned chloroprene polymer is less than 40% by weight, the resulting vinyl chloride resin composition will have a large permanent strain due to compression and tension, and its mechanical strength will also decrease. 40 to 100% by weight is preferred. The effective amount to be added is 5 to 200 parts by weight per 100 parts by weight of the vinyl chloride resin, as the resistance to permanent deformation due to compression and tension is significantly improved, and workability and mechanical strength are also maintained. 20 to 100 parts by weight is preferred.

The vinyl chloride resin used in the present invention includes vinyl chloride,
Or it is a polymer of a mixture of vinyl chloride and a small amount of one or more copolymerizable monomers, and its production method can be any one of bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, etc. You may use any method. Monomers that can be copolymerized with vinyl chloride (°C) include α-olefins such as ethylene and propylene, vinyl acetate, vinyl esters of vinyl stearate, vinyl ethers such as methyl vinyl ether and lauryl vinyl ether, methyl acrylate, and methacrylate. Acrylic acid and methacrylic acid esters such as methyl acid, amides such as methacrylamide and acrylonitrile, nitriles, styrene, α
- Contains styrenes such as methylstyrene, and polyfunctional monomers such as diacrylphthalate and ethylene glycol dimethacrylate.

The plasticizer is not particularly limited, and as in the case of conventional soft vinyl chloride resins, types include heptalic acid esters such as di-2-ethylhexyl phthalate and dibutyl phthalate, and di-2-ethylhexyl phthalate. - Adipic acid esters such as ethylhexyl adipate, sebacic acid esters such as dibutyl sebacate, trimellitic acid esters such as tri-2-ethylhexyl trimesotate, and epoxy compounds such as epoxidized soybean oil are used. The amount added is not particularly limited, but it is 20 to 1 part by weight per 100 parts by weight of vinyl chloride resin.
A suitable amount of 50 parts by weight is used depending on the plasticization efficiency of the above-mentioned chloroprene polymer and the required hardness, flexibility, physical properties, and moldability of the product.

In addition, other polymeric auxiliaries, such as ethylene-vinyl acetate copolymer, acrylic resin, chlorinated polyethylene,
Polyurethane, chlorosulfonated polyethylene, acrylonitrile-butadiene copolymer, etc. may be added.

In addition to the above, the vinyl chloride resin composition of the present invention includes:
It goes without saying that heat stabilizers, fillers, lubricants, blowing agents, flame retardants, pigments, etc. may be added as necessary.

In order to produce the vinyl chloride resin composition of the present invention, the mixing and molding of the ingredients mainly consisting of vinyl chloride resin, chloroprene polymer, and plasticizer are carried out so that each ingredient is substantially uniformly mixed, Any method may be used as long as it is dispersed, mixed, and kneaded, such as a Henschel mixer,
Tri-blending may be performed using a ribbon blender or the like, and the tri-blend powder may be directly molded, or the mixture may be melted and mixed using an extruder, rolls, etc., and then pelletized and molded.

The molding method may be extrusion molding, injection molding, blow molding, calendar molding, vacuum molding, or the like, depending on the shape and properties of the desired product.

Fields of use of the product of the present invention include hoses, gaskets, leather, films, wire covering materials, etc., and it is particularly preferably used for hoses and gaskets.

In order to further facilitate understanding of the present invention, the present invention will be specifically explained below using Examples and Comparative Examples, but the present invention is not limited by these.

Examples 1 to 6 In a Henschel mixer with a jacket temperature of 95°C,
Add 100 parts by weight of vinyl chloride resin (fr'Nkavinle SH-250-) with an average degree of polymerization of 2500 and 6 parts by weight of barium and zinc fatty acid salt composite stabilizer, and heat at high speed until the temperature of the contents reaches 60°C. Stir and mix, and add a predetermined amount of di-2-ethylhexyl phthalate (hereinafter referred to as DOP).
Add. When the temperature of the contents reached 120°C, cooling was started, and when the temperature reached 50°C, a chloroprene polymer (chloroprene, crosslinking agent, and ethylene glycol dimethacrylate) containing del insoluble in toluene was added to the specified amount shown in the table. Powder obtained by copolymerization reaction) was added in a predetermined amount, stirred for about 5 minutes, and then taken out. The chloroprene polymer used here was obtained by combining a cross-linked toluene-insoluble, glu-containing chloroprene polymer latex described in Japanese Patent Publication No. 47-45773, and a toluene-soluble chloroprene polymer latex polymerized by a conventional method into the desired composition. This is a powdered chloroprene polymer having a total of 42 meshes obtained by mixing the mixture to a desired content, freezing, solidifying, washing, drying, and then impact crushing.

The surface temperature of each vinyl chloride resin composition was 16.
After the composition is wound around the rolls, the composition is kneaded using two rolls at 0°C for 10 minutes. Each test piece was prepared by press-molding this roll sheet, and subjected to hardness, compression set, and permanent elongation tests. The results are shown in Table 1.

Comparative Examples 1 to 6 When no chloroprene polymer was added according to the examples (Comparative Example 1) When chloroprene polymers with a gel content of 0 and 30% by weight were added (Comparative Examples 2 to 5) and gel-containing Table 1 shows the results when 96 overlapping parts of 220 parts by weight of chloroprene polymer were added (Comparative Example 6).

The physical properties were measured as follows.

fil roll processable tri-blend powder 200g at surface temperature 1600C
The powder was put into an inch roll, and the roll processability was evaluated based on the time it took for the powder to wrap around the roll and form a uniform sheet.

Less than 0160 seconds △; Less than 120 seconds on 60 tools
cX22Hr (41 permanent elongation JIS K6301, elongation rate 100% r5 + tensile strength n JIS K6723 (6
) Elongation As is clear from the JIS K6723 table, the vinyl chloride resin composition of the present invention maintains roll processability and mechanical strength equal to or higher than that of conventional kettles, and has improved compression set and permanent elongation. I understand.

Examples 7 to 12 Example 5.6 to 00 parts by weight of vinyl chloride resin (Denka Vinyl 5H-250) I with an average degree of polymerization of 2500, 3 parts by weight of DOP 8, and barium zinc fatty acid salt composite stabilizer.
A predetermined amount of the chloroprene polymer with a kale content of 96% used in Comparative Example 6 was added, and after forming into a roll sheet, a test piece was prepared by press molding and the oxygen index was measured. The results are shown in Table 2.

Comparative Examples 7 to 16 Comparative Example 7 measured the oxygen index of Comparative Example 1, and Comparative Examples 8 to 1
6, in place of the chloroprene polymers of Examples 7 to 12, acrylonitrile-butadiene copolymer (Japan Synthetic Rubber Co., Ltd., TSRN 201) was added in a corresponding predetermined amount, and the oxygen index was measured in the same manner as above. did. The results are shown in Table 2.

It can be seen from Table 2 that the compositions of the present invention have excellent flame retardancy. Therefore, it is a flame-retardant composition that has a higher compression set force "-/J% drilling force S than conventional thermoplastic salt hibinyl-based resin compositions.

Patent Applicant: Denki Kagaku Kogyo Co., Ltd. Procedural Amendments, Sho Sosho Jurisdiction, March 2015, Toichi Patent Office Commissioner, Mr. Kazuinu Wakasugi, Indication of the Case, Patent Application No. 15057 No. 15057, filed in 1982, Name of the Invention: Vinyl chloride system Resin composition 3, relationship with the case of the person making the amendment Patent applicant address 1-4-1 Yurakucho, Chiyoda-ku, Tokyo Detailed explanation of the invention column 5 of the specification, content of amendment 1) Page 3, No. 1 ~Correct "compatibility" in the second line to "compatibility."

2) On page 8, lines 4-5, [tri-2-ethylhexyl trimesotate] is corrected to "tri-2-ethylhexyl trimellitate."

3) In the third line of page 14, "into the stabilizer" is corrected to "into 3 parts by weight of the stabilizer."

Claims (1)

[Claims] 1) A chloroprene polymer 5 containing 100 parts by weight of a vinyl chloride resin and 40 to 100 parts by weight of a toluene-insoluble part.
A vinyl chloride resin composition containing ~200 parts by weight and a plasticizer as main components. 2) The vinyl chloride resin composition according to claim 1, wherein the amount of plasticizer is 2D to 150 parts by weight.