JPH08100093A - Vinyl chlorine resin composition - Google Patents

Abstract

PURPOSE: To obtain a vinyl chloride resin compsn. which has a combination of both properties unattainable by the prior art, i.e., is less likely to produce smoke and hydrochloric acid gas and has very excellent flame retardance without deteriorating the oil resistance, mechanical properties and the like. CONSTITUTION: This vinyl chloride resin compsn. comprises 100 pts.wt. vinyl chloride resin, 30 to 120 pts.wt. ethylene/vinyl acetate/carbon monoxide copolymer or ethylene/acrylic ester/carbon monoxide copolymer, 20 to 120 pts.wt. calcium carbonate having an average particle diameter of not more than 3.0μm, and 1 to 100 pts.wt. other inorganic flame retardant (s).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition which is flame-retardant and excellent in low smoke emission, has a remarkably small amount of hydrochloric acid gas generated during combustion, and has excellent mechanical properties and oil resistance. It is a thing.

[0002]

2. Description of the Related Art Generally, vinyl chloride resin compositions are widely used as electric wire coating materials, building materials, daily necessities, etc. because of their excellent flame retardancy. However, vinyl chloride resin compositions produce a large amount of black smoke when burned, obstructing the field of view, and generate a large amount of hydrochloric acid gas from the early stage of combustion, which harms the human body, which hinders evacuation and fire extinguishing activities. There was a problem that For this reason, research on low smoke generation and low hydrochloric acid gasification of vinyl chloride resin compositions has recently become popular,
Increasingly disclosed by patent application publications and other literature. Conventionally, as a means for reducing smoke generation of vinyl chloride resin compositions, there have been reported vinyl chloride resins or ethylene-vinyl acetate-vinyl chloride copolymer resins containing a large amount of one to several kinds of inorganic flame retardants. However, there were problems with low hydrochloric acid gas resistance, oil resistance, mechanical properties, etc. Also, as a means of reducing the hydrochloric acid content of vinyl chloride resin compositions, a method of incorporating fine particle calcium carbonate and supplementing the hydrochloric acid gas generated at the time of combustion has been performed for a long time, but it has low smoke generation and flame retardancy. There was a problem.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides vinyl chloride which is excellent in low smoke generation, low hydrochloric acid gas resistance, and flame retardancy without deteriorating oil resistance and mechanical properties, etc., which have hitherto been incompatible. A resin composition is provided.

[0004]

According to the present invention, an ethylene-vinyl acetate-carbon monoxide copolymer or an ethylene-acrylic ester-carbon monoxide copolymer 30 to 120 is added to 100 parts by weight of a vinyl chloride resin. Parts by weight, average particle size 3.
A vinyl chloride resin composition comprising 20 to 120 parts by weight of calcium carbonate having a size of 0 μm or less and 1 to 100 parts by weight of another inorganic flame retardant.

In the present invention, the vinyl chloride resin means all polymers having a group represented by CH ₂ —CHCl broadly, and includes vinyl chloride homopolymers, ethylene-vinyl chloride copolymers, vinyl acetate-chlorides. Copolymers of vinyl chloride and other polymerizable monomers such as vinyl copolymers, and modified vinyl chloride homo- and copolymers such as post-chlorinated vinyl chloride polymers, and further chlorinated polyethylene Chlorinated polyolefin similar in structure to vinyl chloride resin. These vinyl chloride-based resins can be used alone or in combination of two or more as the vinyl chloride-based resin component in the vinyl chloride-based resin composition of the present invention.

The ethylene-vinyl acetate-carbon monoxide copolymer or the ethylene-acrylic acid-carbon monoxide copolymer is
In particular, it is added to improve low smoke generation and low hydrochloric acid gas property, and the addition amount is limited to 30 to 120 parts by weight with respect to 100 parts by weight of vinyl chloride resin.
This is because if it is less than 100 parts by weight, low smoke generation, low hydrochloric acid gas resistance and cold resistance are remarkably deteriorated, while if it exceeds 120 parts by weight, flame retardancy and combustibility are remarkably deteriorated.

Calcium carbonate has a particle size of 3.0.
The reason why the particle size is limited to less than or equal to μm is that the low hydrochloric acid gas property is remarkably deteriorated when the particle size exceeds 3.0 μm, and the addition amount is set to 20 to 120 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. If the amount is less than 20 parts by weight, the low hydrochloric acid gas property is remarkably lowered, and if it exceeds 120 parts by weight, the mechanical properties, cold resistance and the like are remarkably lowered. As a matter of course, the calcium carbonate referred to herein includes one that has been surface-treated with a resin acid, a fatty acid, lignin or the like for improving dispersibility.

Examples of the inorganic flame retardant used in the present invention include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, zirconium oxide hydrate, tin oxide hydrate, basic magnesium carbonate and hydrotal. Sites, metal hydrates such as dourinite and borax, antimony trioxide and composite flame retardants based on these, zinc borate, zinc oxide, zinc carbonate, zinc sulfide, zinc silicate and other zinc-based flame retardants, molybdenum trioxide, Examples include molybdenum-based flame retardants such as ammonium octamolybdate, talc, and calcium silicate. The addition amount is required to be 1 to 100 parts by weight in terms of flame retardancy, low smoke generation, low hydrochloric acid gas properties, and general physical properties. . The addition may be carried out alone or in combination of two or more kinds.

The vinyl chloride resin composition of the present invention contains, if necessary, stabilizers, plasticizers, lubricants, inorganic fillers, calcined clay, silicon dioxide, ultraviolet absorbers, antioxidants, processing aids, and crosslinkers, in addition to the above. Auxiliary agents, colorants and the like may be added. In particular, a plasticizer is required to give flexibility, but an ethylene-vinyl acetate-carbon monoxide copolymer or an ethylene-acrylic acid ester-carbon monoxide copolymer has a plasticizing effect. So there is no particular need for mechanical properties,
In order to have outstandingly low smoke generation and low hydrochloric acid gas properties without deteriorating the oil resistance and keep the flexibility in a well-balanced manner, the addition amount is 30 parts by weight or less relative to 100 parts by weight of the vinyl chloride resin. preferable. The plasticizer used is DO
Phthalates such as P, n-DOP, DINP, DIDP and mixed alkyl phthalates, aromatic carboxylic esters such as trioctyl trimellitate and trioctylpyromellitate, fatty acid dibases such as DOA, DOZ and DOS There are various types, such as acid ester type, epoxidized soybean oil, epoxidized linseed oil, etc., TCP, TOP, etc.
Used alone or in combination of two or more.

[0010]

【Example】

<< Examples 1 to 5, Comparative Examples 1 to 10 >> Using the raw materials shown below, the compositions shown in Tables 1 to 3 were kneaded with a 6-inch roll to prepare a roll sheet. A sheet-shaped sample having a predetermined thickness was formed by pressing. These were evaluated according to the evaluation methods shown below. The results are shown in Tables 1 to 3. * Raw materials-Vinyl chloride resin: PVC [average degree of polymerization 1300, Tosoh Corporation TH1300] -Ethylene-vinyl chloride copolymer: PVC [average degree of polymerization 1300, Tosoh Corporation E1300] -Ethylene-vinyl acetate Copolymer-Vinyl Chloride Grafter: EVA-VC [Sumitomo Chemical Co., Ltd. Sumigraft GF-Ethylene-Vinyl Acetate-Carbon Monoxide Copolymer: EV
A-CO [Mitsui DuPont Polychemical Co., Ltd. Elballoy 74]
1] -Ethylene-acrylic acid ester-carbon monoxide copolymer: E-AE-CO [Elvalloy HP5 manufactured by Mitsui DuPont Polychemical Co., Ltd.]
53] Calcium carbonate: CaCO ₃ [average particle diameter 0.1 μm, Shiraishi Industry Co., Ltd. Bigotto 10] CaCO ₃ [average particle diameter 4.0 μm, Shiroishi Industry Co., Ltd. Whiten P30] ・ Inorganic flame retardant : Aluminum hydroxide Antimony trioxide Zinc borate Molybdenum flame retardant [Bowen S manufactured by Kikuchi Color Co., Ltd.
K-26] ・ Stabilizer: barium zinc stabilizer ・ Plasticizer: trioctyl trimellitate epoxidized soybean oil * Evaluation method ・ Oxygen index: JIS K 7201 ・ NBS smoke emission rate: ASTM E662 ・ HCL gas generation rate: JCS No. 53 ・ Tensile strength and elongation: JIS K 6723 ・ Oil resistance: JIS K 6723 (using JIS No. 2 insulating oil)

Table 1 Example 1 2 3 4 5 Composition (parts by weight) PVC 100 100 PVC 100 100 100 E-VA-CO 40 110 E-AE-CO 70 70 110 110 CaCO ₃ 70 110 110 30 50 80 Aluminum hydroxide 20 60 10 Trioxide Antimony 10 10 20 20 20 20 Zinc borate 10 10 20 20 20 Molybdenum flame retardant 5 30 Ba-Zn stabilizer 5 5 5 5 5 Trioctyl trimellitate 10 5 5 Epoxidized soybean oil 2 2 2 2 2 Properties Oxygen index 36 30 38 37 35 NBS smoke generation (Dn value) 95 94 68 58 67 Hydrochloric acid gas generation (mg / g) 88 42 95 62 43 Tensile strength (MPa) 20.0 18.5 18.4 17.2 17.4 Elongation (%) 260 280 290 330 340 Oil resistance (70 ℃ × 4hrs) Tensile strength residual rate (%) 93 94 95 91 92 Elongation residual rate (%) 90 90 92 94 95

Table 2 Comparative Example 1 2 3 4 5 Composition (parts by weight) PVC 100 100 PVC 100 EVA-VC 100 100 E-VA-CO 10 CaCO ₃ 60 70 10 60 Aluminum hydroxide 10 70 10 70 70 20 Antimony trioxide 20 20 20 20 20 10 Zinc borate 10 10 10 10 10 Molybdenum flame retardant 5 Ba-Zn stabilizer 5 5 5 5 5 Trioctyl trimellitate 60 60 50 Epoxidized soybean oil 2 2 2 2 2 Characteristic oxygen index 31 36 36 40 32 NBS Smoke emission (Dn value) 155 105 88 65 132 Hydrochloric acid gas generation (mg / g) 75 150 35 130 71 Tensile strength (MPa) 13.2 13.5 9.8 9.5 14.2 Elongation (%) 280 290 265 255 300 Oil resistance (70 ° C) × 4hrs) Tensile strength residual rate (%) 82 85 15 13 85 Elongation residual rate (%) 75 76 53 47 78

Table 3 Comparative Example 6 7 8 9 10 Composition (parts by weight) PVC 100 PVC 100 100 100 100 100 E-VA-CO 70 E-AE-CO 150 70 70 70 70 CaCO ₃ 90 10 70 70 CaCO ₃ 60 Aluminum hydroxide 10 50 20 20 90 Antimony trioxide 20 20 5 10 Zinc borate 20 10 10 Molybdenum flame retardant 5 5 5 Ba-Zn stabilizer 5 5 5 5 5 Trioctyl trimellitate 5 5 5 5 Epoxidized soybean oil 2 2 2 2 2 Characteristics Oxygen index 29 38 33 27 37 NBS smoke amount (Dn value) 68 72 85 120 45 Hydrochloric acid gas generation amount (mg / g) 38 110 105 75 103 Tensile strength (MPa) 9.8 18.2 18.5 17.2 9.8 Elongation (%) 330 305 300 302 270 Oil resistance (70 ℃ × 4hrs) Tensile strength residual rate (%) 95 92 90 91 89 Elongation residual rate (%) 92 91 92 93 87

[0014]

As shown in the table, the vinyl chloride resin composition of the present invention has a low smoke generation property, a low hydrochloric acid gas content and a low hydrochloric acid gas content without lowering the oil resistance and the mechanical strength, which have not been compatible with each other. It has extremely excellent flame retardancy, especially when used as a coating material for electric wires used in buildings,
It is expected that evacuation and fire extinguishing activities during a fire will become extremely easy, and the effect of the present invention is extremely remarkable.

Claims (1)

[Claims] 1. To 100 parts by weight of vinyl chloride resin,
Ethylene-vinyl acetate-carbon monoxide copolymer or ethylene-acrylic acid ester-carbon monoxide copolymer 30 to 1
20 parts by weight, 20 to 120 parts by weight of calcium carbonate having an average particle diameter of 3.0 μm or less, and other inorganic flame retardants 1-1.
A vinyl chloride resin composition comprising 100 parts by weight.