JPS5879034A - Flame-retardant - Google Patents

Abstract

PURPOSE:A novel flame-retardant having a flame-retardant effect, having such impact resistance of resin base as not to be damaged even at high molding temperature, slightly being colored, comprising a salt of a specific heterocyclic compound, being added to the resin base. CONSTITUTION:The desired flame-retardant comprising a salt of a heterocyclic compound (e.g., a salt of 2,3-dihydro-3-oxobenzoisosulfonazol, etc.) shown by the formula(X1 and X2 are H, or halogen; M is alkali metal or alkaline earth metal; m is a valence of M). In using it, 100pts.wt. resin base[a resin base consisting of a (co)polycondensate of an aromatic dihydroxy compound and an ester- forming dibasic acid]is blended with preferably 0.01-5pts.wt. flame-retardant and preferably 0-5pts.wt. organic halogen compound, to give a flame-retardant resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to flame retardants, and in particular to novel flame retardants comprising salts of certain multi-accumulative compounds.

Regarding flame retardants for aromatic resins typified by aromatic polycarbonates, there have already been published US Pat.
It is known that salts of alkali metals or alkaline earth metals have a uniquely excellent flame retardant effect. The uniquely superior flammability effect means that a combustible tree composition with a high level of flammability can be obtained with an extremely small amount of addition. The fact that it shows a flame retardant effect only on the above-mentioned lll1l, which is typified by aromatic polycarbonate, and shows almost no flame retardant effect on other objects is also 6% different. However, some of the flame-retardant resins that are currently in practical use using such technology suffer from a decrease in molecular weight due to expensive molding equipment, which impairs the characteristic impact resistance of the substrate9), and many of which have a strong tendency to color are damaged. It is an object of the present invention to provide a flame-retardant resin composition that is difficult to use, has no tendency to color, and has good transparency.

According to the invention, the general formula [l] X.

(General formula CI), xl and X are each a salt of a hydrogen-containing compound, and a novel flame retardant is provided. General formula C
The complex compound in which X and XI in I) are both hydrogen is generally a substance well known under the name saccharin6, and its alkali metal salts are also known as soluble saccharin. Since alkaline earth metal salts have lower water solubility than alkali metal salts, they are produced by double decomposition of an alkali metal salt of saccharin and a water-soluble salt of an alkaline earth metal. Here, the alkali metals refer to elements belonging to the 11th element in the periodic law of the elements, and examples of those that can be used industrially include lithium, sodium, potassium, and rubidium. Alkaline earth metals also belong to IIaK and include magnesium, calcium, strontium, and barium. A heterocyclic compound in general formula (I) in which xI and/or x is halogen can be produced from toluene in which the nucleus is substituted with halogen according to the method for producing saccharin.

The flame retardant according to the present invention has a flame retardant effect different from that of aromatic polycarbonate. Normally, flame retardancy begins to be observed when a01 part by weight of a flame retardant made by Kinoi@ is added to 100 parts by weight of a resin substrate, and a practically remarkable flame retardant effect is found when a1 part by weight is added. Although an improvement in flame retardancy is observed until 5 parts by weight or more is added, adding more than that increases the inherent excellent properties of the resin matrix, i.e., impact resistance,
This is disadvantageous because it impairs transparency or non-coloring properties. The organic halogen compound itself has a flame retardant effect on the target resin of the present invention, but in order to obtain practically effective flame retardancy, K must be added in large amounts to the extent that it impairs the properties of the substrate. There was a need and a problem. However, the salt of the complex compound according to the present invention and the organic halogen compound have a mutually effective effect on flame retardancy (in the case of each alone), but also the sacrificial relationship necessary to obtain the same flame retardant effect. It is often kept to a minimum. Usually, the amount of the organic compound added at the same time is up to 5 parts by weight per 100 parts by weight of the resin substrate, and addition of more than that is unnecessary.

As the salt of a heterocyclic compound effective in the present invention, 2.3
-dihydro-3-oxo-penziisosulfonazole salt, 2,3-dihydro-3-oxo-4-fluorobenziisosulfonazole salt, 2,3-dihydro-3-oxo-4-chlorobenziisosulfonazole salt of nazor, 2,3
-dihydro-3-oquino-4-promobenzoin sulfonazole salt, 2゜3-dihydro-3-oxo-6-fluorobenziisosulnazole salt, 2,3-dihydro-3-oxo-6-chloroben Salt of soinsulfonasole, 2e 3-dihydro-3-oxo-6-bromobenzoinsulfonazole salt, -2,3-dihydro-3-oxo-4゜6-cyclobenziisosulfonazole salt , 2.3-dihydro-3-oxo-4,6-dipromobenziisosulfonazole salt, 2゜3-dihydro-3-oxo 4-chloro-6-promobenzosulfonazole group or i; t 2.

Examples include salts of 3-dihydro-3-oquino-4-bromo-6-chloropenzosulfonazole. In addition, organic halogen compounds include hequinachlorobenzene, hexabromobenzene, pentabromotoluene, decabromodiphenyl, hexaptetramodiphenyl ether, decabromodiphenyl ether, perchloropentacyclododecane, tetrabromobisphenol, and tetrabromobisphenol carbonate. Condensate, 3.3', 5.5'-nato510m4,4'-dioxydifhenyl sulfone, tetrabromophthalic acid ester, chlorendosun ester, tris(2,3-dibromopropyl) insia Slate, tris (dibromopropyl) phosphate, tris (2-chloroethyl) phosphate, dibromophenyl glycidyl ether, tribromophenyl dalicidyl ether, tribromoaniline, and the like.

The method for evaluating the dynamics of am is from Und@rwriter in the United States.
5ub by s”Laboratori@s 1ne
It is common to use Ject 94 (hereinafter referred to as UL96) K.

Next, specific examples will be given and explained to further clarify the present invention.

Example 1 200 grams of 2.3-dihydro-3-oxobenzoin sulfonazole (saccharin) and 500 grams of water were mixed into an internal volume of 1. ooo i Pour it into a liter beaker. Heat the beaker while stirring the contents gently to bring the temperature of the contents to 60°C. Now a 309IO concentration aqueous sodium hydroxide solution is gradually added to the beaker. The neutralization point is adjusted with promthymol blue. All insoluble impurities are filtered out and the filtrate is cooled to 5°C to precipitate white crystals. When these are taken out and dried, 2,3-dihydro-3-
Sodium salt of oxobenziisosulfonazole approx.
0 gsum is obtained. (This salt is hereinafter referred to as 4H6H-Na.
Potassium salt of oxopenziisosulfonazole (4H6
H-K) The same rubidium salt (4H6B-Rh) and the same lithium salt (4H6H-Li) are obtained.

Implementation Ga 3 4H6H- in a beaker with an internal volume of 1.000 ml
)ia 100g and 600g of water, heat the beaker while stirring gently, and dissolve 1 of the contents.
1 degree becomes 70℃.

At this point, stir a little vigorously and add 200 grams of a 30-g calcium chloride aqueous solution over about 5 minutes. j!
Stir for about 1 hour, cool to room temperature, filter out the white precipitate formed using a conventional method, and wash with 100 grams of water. When this white precipitate is dried, approximately 92 grams of white powder is obtained. This is 2,3-dihydro-3-oxobenziisosulfonazole calcium water (4H6H-Ca).

Example 4 According to Example 3, the magnesium salt of 2,3-dihydro-3-okinepenziisosulfonazole (4H6H-k
II), strontium salt (4H6H-8r) and barium salt (4H6H-Ba) are obtained.

Example 5 200 grams of 2.3-dihydroxy-3-oxo-4-chlorobenziisosulfonazole and 500 grams of water were placed in a beaker with an internal volume of 1.00.0 ml and treated with potassium hydroxide in the same manner as in Example 1. Approximately 205 grams of the above potassium salt are obtained. (Hereinafter, this salt will be referred to as Example 1 (according to the D expression, 4α6H-).) Execution N6 Execution 1 According to FI5, and according to !13J of each Example, 4
Br6H-, 4H6α-, 4H6Br -K
.

% to 4α6α- 4 Br 5 % to Br- 4α5B
r-K.

Salts of compounds of the double cumulative formula, designated as 4Br@α-K and 4F6H-, are obtained.

Example 7 A flame retardant was added to 100 parts by weight of -1300 (product of Teijin Kasei Ltd.) to Panlite, an aromatic polycarbonate resin which is a polycondensate of bisphenol A and carbonic acid, and the mixture was heated at 210°C in a laboratory Brabender. Knead. This is t-280
It is molded using a compression molding machine at ℃ to make a plate with a thickness of x, sm and v meters. From this board length 127 mm and width 13
Cut out a millimeter test piece. The flammability of this is evaluated and graded according to the test method of UI, 96. The rating is in four stages: HB, V-2, V-1, and VO, and the latter is judged to have greater flame retardancy.

Implementation Gafu-1 Implementation 1Pljl or Implementation 1F! Table 1K shows the evaluation of the flame retardant property of the flame retardant obtained in Example 6.

Table 1 Example Gallo-2 Table 2 shows the evaluation of flame retardancy of the samples obtained in Example 1 to Example 1 and subjected to an addition test with an organic halogen compound and an organic halogen compound.

Table-2 Umbrella l; Decaglomodiphenyl ether $2; Tetopromodiphenyl ether $3; IR11 polycondensate of tetrapromobisphenol fi8 A polymer of bisphenol A and terephthalic acid and isophthalic acid with pl bisphenol units. A flame retardant is added to 100 parts by weight of a resin having an average comb barb of 70, and the mixture is kneaded at 290°C in a laboratory Brabender.

This is soldered using a compression molding machine at 300°C to produce a Li meter thick plate. A test piece with a length of 127 mm and a width of 13 mm is cut from this plate, and its flame retardance is evaluated and graded in the same manner as the actual gaff. Table 8 shows the results.

Table-3

Claims (2)

[Claims] (1) General formula CI) Y. (In the general formula (I), xl and X are each a new i1L flame retardant consisting of a salt of a hydrogen cyclic compound. (2) 100 parts by weight of a salt of a compound compound represented by general formula (I) and 30 parts by weight of an organic halogen compound to a, or
A composite IIA fuel consisting of a mixture with oo parts by weight. To 100 parts by weight of a resin substrate selected from
) A flame-retardant*S composition prepared by adding 5 parts by weight of a salt α011 of a compound represented by the compound formula (α011) and 0 to 5 parts by weight of an organic-logen compound.