JPH0551504A - Low smoke emitting soft vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To provide a soft vinyl chloride resin composition having good thermal stability, high flame retardancy, and low smoke-emitting property, by incorporating lauryl diphenyl phosphate as plasticizer, antimony trioxide, zinc oxide, and a polyhydric alcohol as stabilizer aid. CONSTITUTION:The title composition comprises 100 pts.wt. vinyl chloride resin, 30-70 pts.wt. lauryl diphenyl phosphate, 1-30 pts.wt. antimony trioxide, 1-10 pts.wt. zinc oxide, and 0.2-5 pts.wt. polyhydric alcohol as stabilizer aid. This composition emits less smoke and has good thermal stability, flame retardancy, low-temperature flexibility, and heat aging resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a soft vinyl chloride resin composition, and more specifically, it has high heat stability and flame retardancy.
The present invention relates to a soft vinyl chloride resin composition having excellent low smoke generation properties, low temperature flexibility and excellent heat aging resistance.

[0002]

2. Description of the Related Art Generally, a soft vinyl chloride resin composition is widely used in various fields such as various building materials, electric wire coating materials and daily necessities because it has excellent flame retardancy. However, the soft vinyl chloride resin composition has a disadvantage that it generates a large amount of graphite once it is burned, as compared with other polymers, which hinders evacuation and fire extinguishing activities during a fire. Therefore, in recent years, many studies have been made on the smoke reduction of the soft vinyl chloride resin composition, and there have been many reports.

JP-A-60-11543 discloses a vinyl chloride resin composition containing a zinc compound selected from zinc oxide, zinc sulfide, zinc carbonate, zinc silicate and the like for the purpose of reducing smoke emission. Disclosure. However, blending a large amount of such a zinc compound easily causes a so-called zinc burning phenomenon of the vinyl chloride resin composition, and the thermal stability is usually as high as that of the heat stabilizer usually blended in the vinyl chloride resin composition. It has a drawback that it significantly impairs

On the other hand, a vinyl chloride resin composition containing a zinc-based metal soap as a stabilizer is deteriorated and decomposed by light such as heat or sunlight to produce zinc chloride. This zinc chloride causes a so-called zinc burning phenomenon that further accelerates the deterioration of the vinyl chloride resin composition. Therefore, in order to prevent this, the polyhydric alcohol or polyhydric alcohol derivative utilizes the property of trapping zinc chloride, and the polyhydric alcohol or A method of blending a polyhydric alcohol derivative with a vinyl chloride resin is well known.

Japanese Patent Laid-Open No. 1-297448 discloses a vinyl chloride resin containing antimony trioxide, zinc oxide,
Disclosed is a vinyl chloride resin composition containing a polyhydric alcohol stabilizing aid (for example, Planerizer ST210 manufactured by Ajinomoto Co., Inc.). Further, in this specification, phosphate ester-based plasticizers such as tricresyl phosphate and antimony trioxide, zinc oxide, polyhydric alcohol-based stabilizing aids (for example, Plenizer ST21 manufactured by Ajinomoto Co., Inc.)
Although a combination with 0) is described, low smoke generation is not sufficient.

JP-A-2-215850 discloses a flame-retardant vinyl chloride resin composition characterized by containing monoalkyldiphenyl phosphate and magnesium hydroxide as a plasticizer in a vinyl chloride resin for the purpose of making it flame-retardant. Disclose the thing. Further, in this specification, there is shown a formulation in which various inorganic salts are blended with a phosphate ester plasticizer and magnesium hydroxide to obtain a low smoke producing effect. However, low smoke generation was not always sufficient.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a low smoke-producing soft vinyl chloride resin composition which is flame-retardant and has a significantly reduced amount of smoke during combustion without impairing thermal stability. It is to solve the above technical problems.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result of studying a low smoke-producing soft vinyl chloride resin composition using various monoalkyldiphenyl phosphates, It was found that the effect depends on the difference in molecular structure. That is, the straight-chain rather than the branched chain and the long-chain than the short-chain are more effective in lowering smoke emission (however, if the C number of the alkyl chain is too large, the compatibility with the vinyl chloride resin deteriorates and it cannot be used as a plasticizer. The present inventors have completed the present invention by discovering that the number of Cs in the alkyl chain is up to 12), and that various inorganic substances are added to this to have an effect on low smoke emission. That is, the soft vinyl chloride resin composition of the present invention comprises 20 to 150 parts by weight of lauryl diphenyl phosphate, 1 to 30 parts by weight of antimony trioxide, and 1 to 30 parts of zinc oxide per 100 parts by weight of vinyl chloride resin.
10 parts by weight and polyhydric alcohol stabilizing aid 0.2 to 5
It is characterized by blending parts by weight.

The vinyl chloride resin used in the present invention may be an ordinary vinyl chloride resin, regardless of the degree of polymerization.

As a result of a detailed study by the present inventors on the monoalkyldiphenyl phosphate used as a plasticizer, the chain length of the alkyl chain and the presence of the branched chain within a certain limited range result in low smoke emission and compatibility with the resin. It was found to be effective for both solubility. At present, it is widely known to be used as a plasticizer for C8 monoalkyldiphenyl phosphates, and those having an alkyl chain shorter than C8 are not preferable because of low smoke generation effect. Also C
The number 10 has a lower smoke emission than that of the C 8 but is not sufficient. On the other hand, if the C number is 13 or more, the compatibility with the vinyl chloride resin becomes poor. The monoalkyldiphenyl phosphate having a branched chain has a drawback that it has a large amount of smoke generation and that the obtained product lacks thermal stability.

The lauryl diphenyl phosphate used in the present invention is, as a plasticizer, 20 to 150 per 100 parts by weight of a vinyl chloride resin in accordance with various intended uses.
An appropriate amount is added within the range of parts by weight. The smaller the blending amount is, the less the smoke is. However, when the plasticizer effect is added, it becomes harder at 30 parts by weight or less and becomes softer at 150 parts by weight or more, which affects the quality of the product. It is preferably 30 to 70 parts by weight.

The antimony trioxide used in the present invention is
A normal product having a grain size of about 0.1 to 20 μm may be used. Although the blending amount of antimony trioxide varies depending on the intended flame retardant grade of the vinyl chloride resin composition, it is 1 to 30 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, which gives flame retardancy and other physical properties. From the influence, it is preferably 3 to 20 parts by weight.

The zinc oxide used in the present invention may be a normal product having a grain size of about 0.2 to 20 μm. The content of zinc oxide is 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

If the blending amount of zinc oxide is less than 1 part by weight, the smoke suppressing effect is small. On the contrary, if the blending amount of zinc oxide is 10 parts by weight or more, the extension of the smoke suppressing effect stops.

Further, with other zinc compounds such as zinc carbonate,
Compared with zinc oxide, it has a smaller smoke emission suppression effect, and zinc sulfide is difficult to put into practical use with zinc compounds other than zinc oxide, such as sulfide contamination in a system containing a lead stabilizer.

The polyhydric alcohol-based stabilizing aid used in the present invention is a polyhydric alcohol containing at least one kind of pentaerythritol, dipentaerythritol, tripentaerythritol, or the polyhydric alcohol and acetic acid,
Any compound that is a partial ester of a monovalent carboxylic acid such as propionic acid or a divalent acid such as adipic acid or glutamic acid and has one or more hydroxyl groups in its molecule may be used. In this case, the polyhydric alcohol-based stabilizing aid may be a polyhydric alcohol or a partial ester of a polyhydric alcohol and an organic acid, alone or in a mixture thereof. The blending amount is 0.2 to 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, preferably a mixture of a partial ester of dipentaerythritol and adipic acid and a polyhydric alcohol, which has good compatibility with the vinyl chloride resin. A mixture having a polyhydric alcohol content of 10 to 80% by weight (for example, Planerizer ST21 manufactured by Ajinomoto Co., Inc.)
0) is 0.5 to 3 parts by weight.

The soft vinyl chloride resin composition of the present invention may further contain a stabilizer, a lubricant, an inorganic filler, a flame retardant, a colorant and the like other than those mentioned above, if necessary.

[0018]

The soft vinyl chloride resin composition of the present invention reduces the amount of smoke generated during combustion while maintaining flame retardancy when exposed to a flame without impairing thermal stability. Furthermore, it has excellent low temperature flexibility and heat aging resistance.

[0019]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. These examples do not limit the invention.

[0020]

【Test method】

[Preparation of Test Pieces] The compositions of Examples 1 to 4 shown in Table 1 and the compositions of Comparative Examples 5 to 13 shown in Table 2 were placed on a 6-inch oven roll at 160 ° C. for 5 minutes, front roll 11 rpm, rear roll. After roll kneading at 13.5 rpm, 16
Pressed at 0 ° C and 100Kg / cm2 for 5 minutes, thickness 3m
A sheet having a thickness of 0.5 mm, a thickness of 0.5 mm and a thickness of 1 mm was molded.

[0021]

[Oxygen Index] A combustion test (JIS K7201) was performed to determine the oxygen index. As the test piece, a sheet having a thickness of 3 mm was used.

[0022]

[Smoke emission] The surface of the sample is heated with constant radiant heat (2.5 W / cm2) by the combustion furnace installed in the combustion test box. NBS smoke emission tester (Toyo Seiki Seisakusho Co., Ltd.) that optically measures the amount of smoke generated in combination with the flame of the burner that supplied
The amount of smoke generated was measured according to the following formula. As the test piece, a sheet having a thickness of 0.5 mm was used.

[0023]

[Equation 1]

In the above equation, Ds is the visual density, V
Is the volume of the combustion chamber, A is the surface area of the test piece, L is the optical path length, F
0 is the amount of incident light and F is the amount of propagating light.

[0025]

[Thermal stability] The heat stability of the sheet was judged to be good or bad by heating in a gear type oven at 180 ° C. and measuring the time until the sheet discolored and finally became colored black. The test piece is 0.
A 5 mm sheet was used.

[0026]

[Low temperature flexibility] Crashberg test (ASTM D-
1043), and low temperature flexibility was evaluated. As the test piece, a 1 mm sheet was used.

[0027]

[Heat resistance aging] Tensile test after heating (JIS K672
According to 3), the heat aging resistance was measured. Thickness of test piece is 1
mm sheet was used.

The results obtained are shown in Tables 1 and 2.

[0029]

[Table 1]

[0030]

[Table 2]

According to Examples 1 to 4, the thermal stability is impaired by using a mixture of lauryl diphenyl phosphate, antimony trioxide, zinc oxide, and a polyhydric alcohol-based stabilizing aid such as Planerizer ST-210. Without
The oxygen index was prevented from lowering, and excellent low smoke emission was obtained.
Further, the effect was observed in low temperature flexibility and heat aging resistance.

On the other hand, from the results of the comparative examples, alkyldiphenyl phosphates other than lauryl diphenyl phosphate, antimony trioxide, zinc oxide, and prelizer ST
When a mixture of polyhydric alcohol-based stabilizing aids such as -210 is used together, a sufficient low smoke generating effect cannot be obtained. In addition, antimony trioxide, zinc oxide, and planer riser ST-
When a mixture of polyhydric alcohol-based stabilizing aids such as 210 is replaced with magnesium hydroxide, a low smoke generation effect is obtained, but the oxygen index is not improved.

[0033]

Industrial Applicability As described above, lauryl diphenyl phosphate is used as a plasticizer in place of the conventional blending of a soft vinyl chloride resin composition, and it is used in combination with antimony trioxide, zinc oxide, and Planerizer ST-210. It is possible to obtain a soft vinyl chloride resin composition having excellent low smoke generation and excellent low temperature flexibility and heat aging resistance without impairing flame retardancy by using a mixture of a polyol-based stabilizing aid together. It has become possible. As a result, it can be widely used as a low smoke-producing vinyl chloride resin composition in various fields such as various building materials, electric wire coating materials, daily necessities, etc., and evacuation and fire extinguishing activities during a fire become easier than ever before.

Claims (2)

[Claims] 1. To 100 parts by weight of a vinyl chloride resin, 20 to 150 parts by weight of lauryl diphenyl phosphate, 1 to 30 parts by weight of antimony trioxide, 1 to 10 parts by weight of zinc oxide, and 0.1. A soft vinyl chloride resin composition comprising 2 to 5 parts by weight. 2. The polyhydric alcohol-based stabilizing aid is (a)
The low smoke-producing soft vinyl chloride resin composition according to claim 1, which comprises a polyhydric alcohol, (b) a partial ester of a polyhydric alcohol and an organic acid, or a mixture of (a) and (b).