JPS6166747A - Self-extinguishing polycarbonate composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Waru.

According to the technical literature, various methods are known for imparting self-extinguishing properties to polycarbonates. However, many of these are unsatisfactory in that they impair other properties of the polymer.

The self-extinguishing properties of carbonates are improved, for example, by the use of relatively high levels of non-rogenated organic compounds as additives, either in combination with antimony oxide or alone.
J, T, Howarth et al. “Plastic World” J6 4-
7 p. 4, March, 1973). However, the use of such additives results in excessive degradation of the polycarbonate during processing (U.S. Pat. No. 3,334,154);
On the contrary, it is known that the typical basic properties of the polymer are deteriorated (US Pat. No. 4,153,595).

It has been proposed to use tetrahalogenated derivatives of bisphenol A as comonomers in the copolymerization with bisphenol A to produce polycarbonates.

In this case too, it has been reported that in order to obtain good flame resistance, such polymers must contain extremely large amounts of nitrogen. This results in the following drawbacks:

i) Workability is considerably reduced. Therefore, the mechanical properties cannot reach the levels typical of non-halogenated polycarbonates.

11) Generating hydrogen or hydrogen halides under normal production conditions, resulting in corrosion of machinery.

iii) the evolution of large amounts of halogenated destruction products and especially hydrogen halides under combustion conditions, which have a corrosive effect on the metal structure;

According to recent findings, it is also known that the self-extinguishing properties of polycarbonates can be improved by adding small amounts of special organic compounds, such as alkali metal or alkaline earth metal salts of aryl or alkyl sulfonic acids and their derivatives. (For example, U.S. Patent Nos. 3,940,366, 3,933,734, 4,104,253, 4,153,195, and 4,214,062)
.

European Patent Application No. 83200782, No. 7 (1)
June 2, 983) and the same patent application No. 83201215
, No. 7 (August 22, 1983), the inventors disclosed that the Periodic Table of Groups 1A, 1B, IIA, and JI
Salts and ammonium salts of metals belonging to group B, salts of special carboxylic acid compounds or salts of mixtures thereof can be used to improve polycarbonate without impairing its thermal stability and other typical properties under the conditions of production and use. It has been reported that self-extinguishing properties can be improved.

Furthermore, 1 selected from organic and/or inorganic compounds
It has also been reported that the self-extinguishing properties of polycarbonate can be further improved by using a salt of an organic carboxylic acid compound and a salt of an organic carboxylic acid compound.

The inventors newly proposed that the Periodic Table 1 and/or IIA
and salts of special inorganic compounds of metals of group B (used alone or in mixtures with each other and, if necessary, with auxiliaries) meet the UL-9 issued by Polycarbonate.
It was discovered that the present invention can be improved to the highest level shown in the UL-94 standard described in 4Bulletin, and the present invention was achieved. Note that the polymerizable substance is treated with V-Ol according to its behavior.
It was evaluated as V-1 and V-2.

These salts have the general formula M(X)n, (XSO3),
M.

M(NO3)n1M(CNO),,M(SCN)n,1
M[Fe(CN)6).

(In the formula, X is a halogen, M is a periodic table 1
or ① a metal of Group A and B, where n is 2). Suitable such salts include potassium bromide, potassium fluorosulfonate, potassium chlorosulfonate, calcium/umium chlorosulfonate, zinc chlorosulfonate, potassium bromate, sodium bromate, potassium iodate, potassium nitrate, nitric acid. These include sodium, potassium cyanate, potassium thio7anate, sodium thiocyanate, and potassium ferrocyanide.

The auxiliary agents are: 1) Oligomeric or polymeric halogenated N-methyl, 11) An oligomer of phosgene and tetrahalogenated bisphenol A having a phenyl end group and/or an ether of tetrahalogenated bisphenol A and a carboxyl organic acid. , iii) halogenated polyethylene, and iv) an organic halogenated compound selected from halogenated imides.

Suitable adjuvants include octabromodiphenyl oxide, thecabromodiphenyl oxide, 1,2-bis(2,4,6-)lipromophenoxy)-ethane, and tetrabromobisphenol A-bis-(2 , 3-dibromopropyl ether), brominated polyphenylene oxide (
67%), phosgene and tetrabromobisphenol A (n
=3 to 6), tetrabromobisphenol A-bis-(2-hydroxy7ethyl ether)-bis-acrylate, polytetrafluoroethylene, and N,N'-ethylene-bis-tetrabromophthalimide.

The adjuvants may be individually and/or of the same type and/or as mentioned above.
or used as a mixture with other adjuvants of different types.

Periodic Table I and/or I of the special inorganic compounds mentioned above
Salts of metals belonging to Groups IA and B are used in the presence of adjuvants in an amount of 3 phr, preferably less than 0.6 phr (furthermore, two or more salts mixed with each other may be used). when the amount of each salt is further reduced), while in the presence of adjuvants, the amount of 2 phr or less,
It is preferably used at a level of 0.4 Qhq or less.

Individual adjuvants or mixtures thereof are used in amounts up to 3 phr, preferably up to 0.8 phr.

Addition of such additives will result in a viscosity average molecular weight of 10.0.
00 to 100,000, preferably 20,
000 to 50,000, in particular aromatic diols and evabisphenol A-[2,2-bis(4-hydroxyphenyl)-propane] and precursors of carbonate groups. Valid for polycarbonates prepared by reaction. The preparation of polycarbonates by known interfacial polycondensation is usually carried out in the presence of molecular weight regulators, acid acceptors and catalysts.

A commonly used precursor of the carbonate group is carbonyl chloride, although other halides, haloformates or carboxylic acid esters are also used in processes carried out in the absence of solvents. In addition to bisphenol A, bisphenols include bis-(4-hydroxyphenyl)-
Methane, 2°2-bis-(4-hydroxy-3-methylphenyl)-furopane, hydroquinone, resolunol, bis-(4-hydroxyphenyl)-para-diinpropylbenzene can be used.

Polyfunctional aromatic compounds having at least three functional groups can also be used to produce branched polycarbonates.

Of course, two or more bisphenols can also be used. The products obtained according to the invention are used as flame retardant agents not only for linear polycarbonates, but also for branched, mixtures thereof or polymerizable alloys containing polycarbonates. Polycarbonate is a pigment, thermal-oxidative stabilizer, and dye.

It is also possible to include other additives such as fillers, UV absorbers, etc.

Details of operation will become clear from the examples below. It should be noted that the purpose of these Examples is only to explain the present invention, and is not intended to limit the spirit thereof.

Examples 1 to 61 100 parts of aromatic polycarbonates prepared by reaction between bisphenol A and phosgene) were mixed with the additives and auxiliaries shown in the table below.

The mixture of additives and polycarbonate, previously homogenized by grinding in a Re4sch mill, was heated to about 260°C.
into an extruder heated to , the extruded material is cooled,
Granulated.

The granules were formed by both compression molding (285°C, 40 kg/ciii) and injection molding at about 300°C,
A different type of test piece, namely test piece A (approximately 127 x 1
2.7
27X 6,5 X 3,2 birds) and test piece C (65X
55×3, 2 dishes) were obtained.

Five specimens A for each composition shown in the table were subjected to a flammability test for material evaluation according to the Underwriters Laboratory's UL-94 standard. is evaluated as v-o, V-1, V-2 based on the results for five test pieces according to the following criteria.

94V-0: None of the specimens shall exhibit a burn time longer than 10 seconds after being exposed to the Bunsen burner flame. The total burning time for the 5 specimens (10 flame contacts) must not exceed 50 seconds.

None of the test specimens should produce a combustion drip that would ignite the surgical cotton wool placed between 305 vertically below the test specimen.

94V-1: None of the test specimens shall exhibit a burn time longer than 30 seconds after exposure to the Bunsen burner flame. The total burning time for the 5 specimens (10 flame contacts) must not exceed 250 seconds.

None of the specimens should produce a combustion drip that would ignite surgical cotton wool placed 305 mm vertically below the specimen.

94V-2: None of the specimens shall exhibit a burn time longer than 30 seconds after application with the Bunsenper Nano flame. The total burning time for the 5 specimens (10 flame contacts) must not exceed 250 seconds.

The test specimen must not produce a combustion drip that would ignite the surgical cotton wool placed vertically below the test specimen.

Additionally, all five specimens must pass the UL-94 test. Otherwise, these specimens will be evaluated relative to the bad specimens. For example, even if specimen III exhibits V-2 behavior and the other four specimens exhibit V-O behavior,
All five specimens are rated V-2.

If the specimen continues to burn for more than 30 seconds after removal of the Bunsen burner flame, it will not be evaluated under the UL-94 standard. However, regarding the present invention, it is indicated as "flammable".

Test piece B was subjected to a flammability test according to the ASTM D2863-77 standard. The flammability of a polymer is correlated to the concentration of oxygen in the atmosphere in which the specimen is placed. This correlation is expressed as the LCII (Limiting Oxygen Index), the lowest oxygen concentration that can support combustion of the specimen under a nitrogen-oxygen atmosphere supplied from below upward to the specimen.

Specimen C was subjected to light transmission measurements using an XL 211 Gardner device.

To further elucidate the invention, for untreated polycarbonate (designated as "control" in the table) and for polycarbonate to which a salt of an inorganic compound according to the invention, alone or in combination with adjuvants, has been added. The results of the measurements performed are shown in the table below.

(Transparent polycarbonate) R control (additive-free polycarbonate)
263 771 Potassium bromide (0,1)
98 262 Potassium fluorosulfonate (0,1) 39
93 Chlorosulfone 1illJ'7mu (0
,2) 107 25
6 Potassium bromate (0,1)
76 237 same
top (0,25)
31 98 Sodium bromate (0,3)
37 1 Q9 Potassium iodate (0
,1) 61
2010 Potassium nitrate (0,1)
70 24
11 Same as above (0,3)
36 10
I2 Sodium nitrate (0,3)
68 2013
77/acid potassium (0,05)
54 1614 Potassium thioanate (0,01)
l 1615 Same as above
(0+03)
30, 98 flammable
26 5,5 88.94
V-2315,687,70V-0346,087,5 2V-2306,285,7 5V-2306,1-- 5V-2306,0-- s V-2325,787,30V-0
355,986,2 0V-0346,084,0 0V-1345,686,9 0V-1326,085,7 0V-0336,3-- OV-1326,5-- o V-1335,987,83V-23
05,988,4 0V-0356,688+0 Table (continued) (Transparent polycarbonate) Potassium iodate Decabromodiphenyl
391O(0,07) oxide
(0,1)l potassium nitrate')A(0,025)
102
25≧ Same as above (Q, 025) Same as above (0,3
) 35 9) Same as above (0,07
) Octabromodiphenyl 27
9 Oquindo (0,1) [Potassium nitrate (0,07) Tetrabromobisphenol 41 10A-bis-(2
,3-dibromopropyl ether) (0,1); /potassium annate (0,035)
63 16) Same as above (0,03
5) Decabromodiphenyl ookindo (0,1)
24 7 Potassium theocyanate
6716 mu
(0,01) -R1",!"i - OV-0365,687,8 2V-2305,887,3 0V-0345,987,0 0V-0366,186,4 0V-0366,+86,1 1 V-2315, 987, 80V-035
6,087,5 3V-2305,988,4

Claims (1)

[Claims] 1 A) General formula M(X)_n, (XSO_3)_nM,
M(XO_3)_n, M(NO_3)_n, M(CNO
)_n, M(SCN)_n, M[Fe(CN)_6]_
No. 1 and/or No. 1 of the Periodic Table, represented by n (wherein, IIA and B
at least one additive selected from the group consisting of inorganic compound salts of metals belonging to the group B) i) oligomeric or polymeric halogenated ethers, ii) phosgene and tetras with phenyl end groups; an oligomer of halogenated bisphenol A and/or an ether of tetrahalogenated bisphenol A and a carboxy organic acid; iii) halogenated polyethylene; and iv) at least one auxiliary agent selected from the group consisting of halogenated imide. A self-extinguishing polycarbonate composition characterized by: 2. In the product according to claim 1, the component A) is preferably potassium bromide, potassium fluorosulfonate, potassium chlorosulfonate, calcium chlorosulfonate, zinc chlorosulfonate, potassium bromate, bromine. A self-extinguishing polycarbonate composition selected from sodium acid, potassium iodate, potassium nitrate, sodium nitrate, potassium cyanate, potassium thiocyanate, sodium thiocyanate, and potassium ferrocyanide. 3. In the product according to claim 1, said component B) is preferably octabromodiphenyl oxide, decabromodiphenyl oxide, 1,2-bis(2,
4,6-tribromophenoxy)-ethane, tetrabromobisphenol A-bis-(2,3-dibromopropyl ether), brominated polyphenylene oxide (Br=
about 67%), phenyl-terminated oligomers consisting of phosgene and tetrabromobisphenol A (n=3 to 6), tetrabromobisphenol A-bis-(2-
A self-extinguishing polycarbonate composition selected from among (hydroxyethyl ether)-bis-acrylate, polytetra, fluoroethylene, N,N'-ethylene-bis-tetrabromophthalimide. 4. In the absence of said adjuvant, said component A) is present in an amount of no more than 3 phr, and in the presence of an adjuvant, said component A) is present in an amount of no more than 2 phr. Self-extinguishing polycarbonate composition. 5. According to claim 4, in the absence of adjuvants, said component A) preferably has a concentration of 0.6ph.
A self-extinguishing polycarbonate composition, which in the presence of adjuvants is present in an amount of no more than 0.4 phr. 6. A self-extinguishing polycarbonate composition according to claim 1, wherein component B) is present in an amount of 3 phr or less. 7. A self-extinguishing polycarbonate composition according to claim 6, wherein component B) is present in an amount preferably not more than 0.8 phr. 8. In the item set forth in any one of claims 1 to 7, periodic table No. 1 and/or IIA
and a self-extinguishing polycarbonate composition, wherein said metals of group B are preferably sodium and potassium.