JPH0324135A - Flame-retarding organic polymer composition - Google Patents

Abstract

PURPOSE:To obtain an organic polymer composition excellent in flame retardancy, heat resistance and safety by mixing an aromatic phosphoric ester compound with a specified hydroquinone compound and an organic polymer. CONSTITUTION:A flame-retarding organic polymer composition comprising an aromatic phosphoric ester compound, a hydroquinone compound of the formula and an organic polymer. In the formula, R1, R2, R3 and R4 are each H or a 1-14C alkyl. Examples of the hydroquinone compounds especially excellent in heat resistance include 2,5-di-t-amyl-hydroquinone and 2,5-di-t- butylhydroquinone. The aromatic phosphoric ester compound is used in an amount of 1-50 pts.wt. per 100 pts.wt. organic polymer. The hydroquinone compound is used in an amount of 0.01-10 pts.wt. per 100 pts.wt. aromatic phosphoric ester compound. This composition can be effectively used as a material for electrical products, automobile trims, textile products, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a flame-retardant organic polymer combination excellent in both flame retardancy and heat resistance (discoloration prevention, deterioration prevention, etc.).

(Prior Art) Organic polymers such as thermoplastic resins such as polypropylene, polystyrene, and acrylonitrile butadiene styrene (ABS) resins; and thermosetting resins such as polyurethane and phenol are relatively inexpensive and easy to obtain. Because they have excellent properties such as being easy to shape, they are widely used in all kinds of household goods, including electronic parts and automobile parts. However, these organic polymers are easily flammable, so once a fire breaks out, they easily burn and dissipate.

Cable fires have a particularly big impact on society.

Today, some of the fields in which organic electrolyte composites are used include electrical products, automobile interior parts, and textile products. Flame retardant is required by law. For example, U in electrical products in the United States
The flame retardant regulations of L standard and MVSS-302 related to white motor vehicles are known.

In order to impart flame retardancy to organic polymers, flame retardants must be added during the preparation of resins or molded articles; flame retardants must be added to inorganic compounds. There are organic phosphorus compounds, organic halogen compounds, and halogen-containing organic phosphorus compounds.In particular, organic halogen compounds and halogen-containing phosphorus compounds exhibit excellent flame retardant effects. However, such halogen compounds decompose thermally and generate hydrogen halides when molded into resin, corroding the mold, degrading the resin itself, and causing other problems.
Coloration occurs. Furthermore, there is also the problem of deteriorating the working environment. Plastics containing halogen compounds have become a social problem because they generate the highly toxic dioquine when burned, and there is an increasing demand for flame retardants that do not contain halogens. Flame retardants that do not contain halogen include inorganic compound flame retardants such as aluminum hydroxide and magnesium hydroxide. However, compared to the above-mentioned halogen-containing flame retardants, these compounds Flame retardant effect is extremely low.

In order to obtain a sufficient effect, it is necessary to add a large amount of the above-mentioned compound, which has the disadvantage that the original properties of the resin are impaired. Contains no halogen. It is a flame retardant that provides a relatively good flame retardant effect and does not significantly change the physical properties of the resin. Organic phosphorus compounds are used.

in general. The above organic phosphorus compound is j. Fifth, when flame-retardant resin assemblies containing various flame retardants are molded, the resin discolors and deteriorates. Poor heat resistance. This is mainly due to thermal decomposition of the flame retardant. In recent years, engineering brass. Furthermore, the development of high-performance glass materials such as super engineering plastics is progressing. Since these plastics have a high molding temperature, there are great demands on the heat resistance of the flame retardant resin assembly. As a method to improve the heat resistance of resin,
There is a method in which ordinary antioxidants (such as pentanol compounds, sulfur compounds, and amine compounds) are added to organic polymers along with flame retardants. However, such antioxidants, e.g. Along with the above organic phosphorus compounds,
Also when added to organic polymers. At temperatures of 200°C or higher, coloration of the dipolymer was unavoidable.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned conventional problems, and its purpose is to provide a flame-retardant organic polymer assembly that is excellent in both flame retardancy and heat resistance. The purpose is to provide something. Another object of the present invention is to provide a flame-retardant organic polymer composition with excellent safety.

(Means for Solving the Problems) The present invention uses a hydroquinone compound as a specific antioxidant in order to improve the heat resistance of aromatic phosphate ester compounds with excellent flame retardant effects. The invention was completed based on the inventor's knowledge that by adding the compound to an organic polymer together with an aromatic phosphate ester compound, heat resistance can be significantly improved while maintaining flame retardancy.

The flame-retardant organic polymer composition of the present invention is an aromatic phosphate ester compound, a hydroquinone compound represented by formula (I). and an organic polymer, whereby the above object is achieved: where Rl. R2, R3 and R
4 is each independently hydrogen or has 1 to 1 carbon atoms;
14 is an alkyl group.

Examples of the organic polymer contained in the flame-retardant organic polymer &lIy'fc product of the present invention include. Polyethylene, polypropylene, polybutadiene, polystyrene resin, impact-resistant polystyrene, polyvinyl chloride, ABS resin, polyphenylene oxide resin, polymethyl methacrylate. polyamide. Polyester and polycarbonate are available. These resins may be modified with resin modifiers (phenylmaleimide, maleic anhydride, etc.). Modified plastics include styrene-modified polyphenylene oxide, imide ring-containing ABS resin, modified polyester resin (e.g., PET, PBT), modified nylon resin, modified polycarbonate (PC), and ABS.
/PC Alloy. There are polyphenylene oxide/nylon alloys, which are effective as engineering plastics. The above resin is. One type or a mixture of two or more types may be used. The aromatic phosphate ester compounds contained in the composition include. There are monophosphates and polyphosphates. As monophosphate elf. There are phosphates with one type of aromatic group and phosphates with two or more types of aromatic groups. The above-mentioned phosphates having one type of aromatic group are as follows. Triphenyl phosphate, tricresyl phosphate. Trixylenyl phosphate. Tris(isobrobylphenyl) phosphate. Tris(0-phenylphenyl)phosphate. Tris(p-phenylphenyl) phosphate. Examples include trinaphthyl phosphate. As a phosphate having two or more types of aromatic groups. Phenyl, cresyl, xylenyl, isoprobylphenyl, 0-phenylphenyl, p-phenylphenyl,
There are phosphates that have two or more types of aromatic groups, such as naphthyl. For example, talesyl diphenyl phosphate,
Xylenyl diphenyl phosphate, di(isobrobylphenyl) phenyl phosphate. Examples include 0-phenylphenyl dicresyl phosphate. The above polyphosphates are compounds of the following formula (It) produced by the reaction of an aromatic divalent hydroxy compound, oxophosphorus chloride, and an aromatic monovalent hydroxy compound: where *Rs. R& is an aromatic group. A is a residue of the above aromatic divalent hydroxy compound. n is an integer from 1 to 20. The above aromatic divalent hydroxy compounds include: for example. Hydroquinone, resorcinol, bisfuunol A. Bisphenol F. Bisphenol S can be used. As an aromatic monovalent hydroxy compound. for example. Phenol.
Cresol. Xylenol. Isobrobylphenol.
0-phenylphenol, p-phenylphenol, and naphthol can be used. Note that polyphosphate can also be used in combination with monophosphate. The aromatic phosphate ester compound is the organic polymer 10 mentioned above.
0 parts by weight, 1 to 50 parts by weight, preferably 5 to 30 parts by weight
Contained within the range of parts by weight. If it is less than 1 part by weight, the desired flame retardancy will not be imparted to the resulting flame-retardant organic polymer assembly. If it exceeds 50 parts by weight, not only the flame retardance will not improve much. This has an unfavorable effect on the physical properties of the resulting flame-retardant organic polymer composite. Hydroquinone compound. 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of this aromatic phosphate ester compound.
It is contained within the range of 3.0 parts by weight. If it is less than 0.01 part by weight. The flame-retardant organic polymer #Ii obtained did not have the desired heat resistance. If it exceeds 10 parts by weight.
Although the heat resistance of flame-retardant organic polymer compositions is improved, the flame retardancy is impaired. The above hydroquinone compounds include: For example, hydroquinone, 2,5-di-tert-butylhydroquinone, 2
．． 5-tert-alhydroquinone, 2.5-
Dioctylhydroquinone, tert-amylhydroquinone, tart-butylhydroquinone. Examples include octylhydroquinone. especially. Hydroquinone compounds with excellent heat resistance include 2,5-di-tart-aξ
and 2,5-di-tert-butylhydroquinone. By combining these hydroquinone compounds with the above-mentioned aromatic phosphate ester compounds and incorporating them into an organic polymer. Due to the synergistic effect of both. Organic polymer compositions with excellent flame retardancy and heat resistance can be obtained. ? The mechanism by which oxidation inhibitors such as hydroquinone compounds impart heat resistance to organic turtle polymers is not shown in 6 and 2 below.

Chemical substances in general. Reacts with oxygen and fires ζ active radicals; These active radicals react with other substances and cause thermal deterioration and discoloration. This kind of reaction is the same even if the chemical substance is l# retardant or arithmetic polymer! l:,
For example, it is shown by the 9th order equation.

RH-+-0. −R・+H 0 0・ ・・・0
}R − + O■→ I200・・・・(
2) Here, JH is antioxidant + J: Japan], Zoshi7 J
・It is an inert radical.

For example, the antioxidant is diphenylene. 2. If it is a lua series, then the inert radial formula shown by the following formula (5). Zoshide 2I6-G t. When ert-butybean/tirufu is reacted with nol (a hindered phenolic antioxidant), the inert radical shown in (6) below is generated.

2, R is a chemical substance (e.g. 9 organic polymer), 2
R. and ROO. are active radicals.

Does the antioxidant react with the active radical R or ROO obtained in reaction (1) or reaction (2) above? , generates inert radicals. This inert radical has low reactivity with other substances. Prevents thermal deterioration and discoloration of chemicals. fft> is shown below.

R・+. J H Ika R H + J・・
...(3) ROO・+J H−+R 0 0 H +
J...(4) tert-C4H<i However, if the antioxidant is a hydroquinone compound, a more stable quinone compound is formed from an inert radical through the reaction shown in the following formula (here, 7. Showed the reaction of hydroquinone). This quinone compound is more stable than inert radicals, and can more effectively prevent thermal deterioration and discoloration of chemical substances.

For this reason, the hydroquinone compound used in the present invention is... compared to conventional antioxidants. The heat resistance of the e-f polymer is significantly improved.

The flame retardant organic polymer composition of the present invention includes 1 flame retardants other than aromatic phosphate ester compounds within a range that does not impair physical properties. Antioxidants other than hydroquinone compounds. Additives such as flame retardant aids (eg, antimony trioxide), fillers, pigments, and UV absorbers may also be included.

The flame retardant organic polymer composition of the present invention is an aromatic phosphate ester compound. A hydroquinone compound and an organic polymer are mixed together using the known H method. In this method, for example, an aromatic phosphate ester compound and a hydroquinone compound are added together with monomers during polymerization of an organic polymer. A method of adding these compounds at the time of forming an organic polymer; A method of dissolving a hydroquinone compound in an aromatic phosphate ester compound in advance, and then kneading and forming the organic polymer; Add a hydroquinone compound to the spinal mechanical and electrical combination. There is a method of kneading it with an aromatic phosphate ester compound and molding it.

(Example) The present invention will be described below with reference to Examples. In the examples. All parts are parts by weight.

60 parts of Daigon Gaido poly(2,6-dimethyl-1,4-phenylene) oxide, 40 parts of rubber-modified impact-resistant Borisutine,
10 parts of triphenyl phosphate and 0.1 part of 2,5-di-tert-butylhydroquinone were mixed in a mixer and passed through an extruder maintained at 300°C to obtain compounding pellets. This pellet was placed in an injection molding machine and molded at 290 to 300°C to obtain a test piece. Using this test piece, flame retardancy and
Discoloration and tensile strength were measured.

The flame retardancy of the test piece was determined using the UL-94 test method. The flame retardance of the test pieces was classified into four types: V-0, V-1, V-2, and HB.

Weird hair Discoloration of the test piece was visually determined.

AST is the tensile strength of Ushimata△magnetic test piece? l Measured by D638.

As a result, the flame retardancy was V-Q, and no discoloration was observed.
The tensile strength was 570 kg/cd. These results are shown in Table 1. Example 2 and Comparative Example 1 described below
The results of 2 and 2 are also shown in Table 1. Back application 1 Instead of triphenyl phosphate, tetraphenylphenylene diphosphate (CR-7333 manufactured by Daihachi Chemical Co., Ltd.
) was used to obtain the test piece. The procedure was the same as in Example 1 except that tridecyl phosphite was used instead of 2,5-di-tart-butylhydroquinone to obtain a test piece.

Comparison group 1 The same birch as in Example 2 except that tridecyl aqueous sphite was used instead of 2.5-di-tart-butylhydroquinone to obtain a test piece. 100 parts of main polybutylene terephthalate. 12 parts of cresyl diphenyl phosphate, and 2,5-di-tert
- Mix 0.1 part of amylhydroquinone with a ξxer.
Compound pellets were obtained through an extruder maintained at 280°C. Put this pellet into the injection molding machine, 29
Store at 0-300℃. A test piece was obtained. Using this test piece, flame retardancy was determined in the same manner as in Example 1. Discoloration and tensile strength were measured. These results are shown in Table 2. The results of Example 4 and Comparative Examples 3 and 4, which will be described later, are also shown in Table 2. The same birch as in Example 3 was used, except that tetraphenylphenyl diphosphate was used instead of cresyl diphenyl phosphate to obtain a test piece. The same birch as in Example 3 was used, except that 2,6-di-tert-butyl-p-cresol was used instead of the comparative mottled 2,5-di-tert-alhydroquinone. The procedure was the same as in Example 4, except that a test piece was obtained using 2,6-di-tert-butyl-p-cresol instead of 2,5-di-tert-amylhydroquinone.
Jitsuchonoi 60 parts polycarbonate, 40 parts BS resin. 3 parts of triphenyl phosphate, 9 parts of tetraphenylphenylene diphosphate and 0.1 part of 2,5-di-tert-butylhydroquinone were mixed in a mixer and passed through an extruder maintained at 260°C to obtain a compound pellet. Put this pellet into the injection molding machine. 250-260
Shape at ℃. A test piece was obtained. Using this test piece. Flame retardant was tested in the same manner as in Example 1. Discoloration and tensile strength were measured. These results are shown in Table 3. Table 3 also shows the results of Examples 6 and 7 and Comparative Examples 5 and 6, which will be described later. The test piece was the same as Example 5 except that the test piece was obtained using talesyl diphenyl phosphate instead of triphenyl phosphate. Formula (
The procedure was the same as in Example 6 except that the test piece was obtained using the oligomer represented by n) (n=1 to 10). Kitakianban Engineering 2 * 5 - '; Instead of tert-butylhydroquinone, N,N'-diphenyl p-
The procedure was the same as in Example 5 except that the test piece was obtained using phenylene diane. In place of this amount of 2.5-tert-butylhydroquinone, N. The procedure was the same as in Example 6 except that N'-diphenyl-p-phenyleneamine was used to obtain the test piece. (The following is a blank space) (Effects of the invention) The flame-retardant organic polymer composite sole of the present invention has the following advantages. Excellent in both flame retardancy and heat resistance. Even if this set of precepts is exposed to high temperatures, the precepts will not deteriorate or change color. Therefore, the flame retardant organic polymer &lltc product of the present invention can be used in electrical products. Automotive interior parts. It can be effectively used as a material for textile products. that's all

Claims (1)

[Scope of Claims] 1. A flame-retardant organic polymer composition containing an aromatic phosphate ester compound, a hydroquinone compound represented by formula (I), and an organic polymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) Here, R_1, R_2, R_3 and R_4 are each independently hydrogen or an alkyl group having 1 to 14 carbon atoms. 2. The flame-retardant organic polymer composition according to claim 1, wherein the aromatic phosphate ester compound is contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the organic polymer. 3. The flame-retardant organic polymer composition according to claim 1, wherein the hydroquinone compound is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the aromatic phosphate ester compound.