JPS60149657A - Flame-retardant polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having an excellent property of controlling its dropping in a molten state during combustion, consisting of an arom. polycarbonate resin, a specified potassium org. phosphate, an arom. phosphite ester compd. and an organosilicon compd. CONSTITUTION:0.001-5pts.wt. potassium org. phosphate of the formula [wherein X1-8 are each H, halogen, acryl, (halogen-substd.) aryl, aralkyl], 0.001-0.5pts. wt. arom. phosphite ester compd. such as triphenyl phosphite and 0-0.5pts.wt. org. silicon compd. such as methyltrinonyloxysilane are blended with 100pts.wt. arom. polycarbonate resin obtd. from an arom. dihydroxydiphenylalkane [e.g. 2,2-bis(4-hydroxyphenyl)propane] contg. no halogenated arom. dihydroxydiphenylalkane component. The mixture is kneaded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a lIi-fired polycarbonate composition, in particular a halogenated aromatic dihydroxydiphenylalkane composition containing no halogenated aromatic dihydroxydiphenylalkane component. , to 100 parts by weight of carbonate resin, ta) organic potassium phosphate salt represented by the following general formula (1) 0,0
01 to 5.0 parts by weight, (b) 0.001 to 0.5 parts by weight of an aromatic phosphite compound, and 0 to 0.5 parts by weight of a (Cl organosilicon compound). The present invention provides a resin composition in which x1 to x8 each represent hydrogen, a halogen, an acyl group, an aryl group, an aryl group substituted with a halokene, or an aralkyl group.

The method for making aromatic polycarbonate resin flame retardant is as follows:
Conventionally, organic halogenated compounds, such as Japanese Patent Publication No. 47
-44537 discloses the addition of a polycarbonate oligomer of tetrabromobisphenol A, but adding only such an organic halogenated compound can shorten the combustion time, but prevent the dripping of molten resin during combustion. It cannot be prevented. In addition, in order to sufficiently shorten the combustion time, it is necessary to add a considerable amount of halides, so in the case of an actual fire accident, a large amount of harmful gas and tsubo will be generated during combustion. Met. Furthermore, a series of patents such as JP-A No. 52-54745 and JP-A No. 52-65555 disclose methods of adding salts of organic sulfonic acids. The sulfonates disclosed in these publications are said to have a flame retardant effect, particularly an effect of suppressing dripping of molten resin during combustion, and an effect of suppressing smoke generation. On the other hand, aromatic polycarbonate resins to which such sulfonates are added When molded at high temperatures, a significant polymer decomposition phenomenon occurs, which not only causes a partially foamed appearance and a poor appearance.
Causes a decrease in mechanical strength due to a decrease in molecular weight. To give a specific example, as a sulfonate, the following formula (X in the formula
=Br<m=2, M=K) is problematic in that it causes a foam-like appearance defect in a part of the specially molded product. or,
In the compound of the following formula, the addition of 0.3 wt% increases the molecular ff124,
When molding 000 polycarbonate resin, the molecular weight becomes 1.
APIlA before molding decreased to about 7.000 to 18,000, causing coloring due to significant thermal decomposition during molding.
15 have become more than 500.

Furthermore, in JP-A No. 56-50956, polycarbonate resin has the following general formula (3) (wherein, X is F, CL BrXm is an integer of o to 2,
M is Na, K, Mg, Ca5SrSBa, Z
There is a technique of adding an organic phosphate represented by n, B, AI, n is an integer corresponding to the valence of M) and an oligomer of halogenated bisphenol or a cooligomer of halogenated bisphenol and non-halogenated bisphenol. Disclosed.

Although this technology has been shown to be effective to some extent in suppressing dripping of molten resin during combustion, lowering molecular weight during molding, and reducing coloring, it has not yet achieved the most severe flame retardant level required in the electronics and electrical industries.
It is difficult to stably satisfy υL, 94V-0 of es+ Inc., and Canadian 5standardsA, which is considered to be an even stricter flame retardant standard.
ssociation, Electrical Bull
letin No, 968°C1ause' 6.11
It did not pass the II fuel standard (hereinafter abbreviated as C5AN fuel standard) at all.

The mechanism of the flame retardant value of aromatic polycarbonate resin due to alkali metal salt is as shown in reaction formula (4) below. It is known that the viscosity properties of the molten resin during combustion are improved by decomposing and rearranging bonds to form branched and crosslinked structures such as salsylate bonds.

However, when a large amount of alkali metal salt is added, although a branched/crosslinked structure is formed, the decomposition of the main chain bonds is too accelerated, making it difficult to prevent the molten resin from burning and dripping during combustion. Moreover, silver streaks and the like occur during molding, making it difficult to obtain a good molded product. In addition, when the alkali metal salt is added in an amount that allows a good molded product to be obtained, the amount of branched/crosslinked structures formed is small, and it is difficult to improve the viscosity characteristics of the molten resin during combustion. Not enough. JP-A-52-54745, JP-A No. 52-65555, JP-A No. 56
-50956 and the like have these problems.

The present inventor has completed the present invention as a result of intensive research aimed at improving the conventional drawbacks of flame retardant aromatic polycarbonate resins.

The H-flammable polycarbonate resin composition of the present invention has almost no change in hue or decrease in molecular weight during molding, has a flame retardant effect, especially improves the viscosity characteristics of the molten resin during combustion, and is excellent in suppressing dripping of the molten resin. At the same time, in particular, C5A t
In the standard flame test, conventional flame-retardant polycarbonate resin failed even at a thickness of 3.0 mm, whereas 2.
It has extremely outstanding performance, being able to pass the test even with a fin thickness of 1 to 2.3.

Hereinafter, the configuration of the present invention will be explained in detail.

The aromatic polycarbonate resin of the present invention is an optionally branched thermoplastic polycarbonate polymer made by reacting an aromatic dihydroxy or polyhydroxy compound with a diester of phosgene or carbonic acid. Examples of aromatic dihydroxy compounds include bis(4-hydroxyphenyl)methane, 1. Examples include l-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, and 2,2-bis(4-hydroxyphenyl)butane. In order to obtain homopolymers and copolymers of branched aromatic polycarbonate resins, phloroglucin, 4,6-cymethyl-2,4.
6-tri(4-hydroxyphenyl)hebutene-2
, 4,6-dimethyl-2.4.6-tri(4-hydroxyphenyl)hebutane, 2,6-dimethyl-2.4.
6-tri(4-hydroxyphenyl)hebutene-3
,4,6-dimethyl-2.4.6-tri(4-hydroxyphenyl)butane,1,3.5-tri(4-
hydroxyphenyl)benzene, Ll, 1-tri(4
-hydroxyphenyl)ethane, and 3,3-bis(4-hydroxyaryl)oxindole (=isatin bisphenol), 5-chloroisatin, 5゜7-dichloroisatin,
A part of the aromatic dihydroxy compound, such as 0.2 to 2 mol %, is replaced with a polyhydroxy compound such as 5-bromiisatin. Furthermore, m-aromatic hydroxy compounds suitable for adjusting the molecular weight of homopolymers, copolymers, and oligomers of aromatic polycarbonate resins include m- and p-methylphenol, tri- and p-propylphenol, p-bromophenol, .4.6-) Lipromphenol, p-tert-butylphenol and p
Long-chain alkyl-substituted phenols and the like are preferred. Furthermore, the molecular weight of oligomers and cooligomers can be adjusted by adjusting the reaction conditions, and the reactive terminals can be substituted with thermally stable hydroxyl groups.

The method exemplified by the neutralization reaction between the organic potassium salt of general formula (11) used in the present invention (81 is a compound in which potassium (K) in the general formula (1) is hydrogen and potassium hydroxide) Examples of such compounds include compounds in which X1 to X8 in the general formula (1) are all hydrogen, i where X6 and X8 are chlorine and the other X is hydrogen; , X6, x8 are chlorine and the other X is hydrogen; X6, X8 are bromine and the other X is hydrogen: X2
, X3, X6, and ×8 are chlorine and the other X is hydrogen;
Examples include those in which X6, X8 are bromine and the other X is hydrogen; x6 is bromine, X8 is chlorine, and the other X is hydrogen.

In the present invention, the amount of the compound of general formula (1) added is o, o
If the amount is less than oi part by weight, the flame retardant effect will be insufficient and undesirable, and if it is more than 5.0 parts by weight, the molecular weight of the resin will decrease during molding, the appearance of the molded product will be poor, coloration, etc. will be significant. So I don't like it. From the viewpoint of thermal stability during molding and flame retardant effect, the addition range is more preferably 0.005 to 2.0 parts by weight, particularly preferably 0.01 to 1.0 parts by weight.

Aromatic phosphite compound fb) used in the present invention
Examples include triphenyl phosphite, tris(nonylphenyl) phosphite, tris(214-diter)
t-Butylphenyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphite, diphenyl monooctyl phosphite, diphenyl-2-ethylhexylbosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra(tridecyl) ) Pentaerythritol tetraphosphite, hydrogenated bisphenol A phosphite polymer, 4,4'-butylidene-bis(3-methyl-
Examples include 6-tert-butylphenyl-di-tridecyl) phosphite, bisphenol A pentaerythritol phosphite, and tetrakis(2,4-di-tert-butylphenyl)-4°4'-biphenylbosphite.

The aromatic phosphite compound in the present invention improves the viscosity characteristics of the molten resin during combustion by appropriately controlling the formation and distribution of branched structures and crosslinked structures in the composition of the present invention. At the same time, it suppresses decomposition of the composition and prevents the occurrence of silver streaks during molding.

The amount of aromatic phosphite compound added is o, 'oo
If it is less than i parts by weight, the above effects will be insufficient, and if it is less than 0.
Even if more than 5 parts by weight is added, the effect will not improve, and 0.001 to 0.5 parts by weight, especially 0.005 to 0
．． A range of 2 parts by weight is preferable.

As the organosilicon compound (C) used in the present invention,
Examples include methyl tri-5eC-octyloxysilane (1), methyltrinonyloxysilane (2), tetra(2-ethylhexyl) silicate (2), tetranonyl silicate (2), tetratridecyl silicate (2), and other organic silicon compounds. A specific example is shown by a formula: ■: C1 et al. 3i (0-CFI-CI(2-Cth -CH
2-CH2,-CH2-C1%)' 3CH3 ■: CH3 I ■: C1+3 ■: Si (-0CI+ll+22) 4, ■: etc. The organosilicon compound reacts with the active end of the polycarbonate induced by the organophosphate potassium salt and helps to efficiently form a branched structure and a crosslinked structure. The amount of the organosilicon compound added is suitably 0 to 0.5 parts by weight, particularly 0 to 0.2 parts by weight, and the effect will not improve if it exceeds 0.5 parts by weight.

The N-flammable polycarbonate resin composition of the present invention as described above may contain other stabilizers, pigments, dyes, various additives such as lubricants, reinforcing materials such as inorganic or organic fiber substances, and glass beads, as desired. Various fillers such as these may be blended, and further, other resin components may be blended within a range that does not impair the characteristics of the present invention. For example, polycarbonate oligomers derived from bisphenol A can be blended to improve moldability and surface properties, and heat-resistant polyesters such as polyester carbonate and polyarylate (for example, trade name: U Polymer, Unitika) can be blended to improve heat resistance. can be mentioned.

In preparing the thermoplastic resin composition of the present invention,
Any conventionally known method may be used, and methods of kneading using an extruder, Banbury mixer, rolls, etc. may be selected as appropriate.

The explanation will be given below using Examples and Comparative Examples.
and "molecular weight" are based on weight unless otherwise specified.

Male side-1 to 6, Comparative examples-1 to 3 2. Organic phosphoric acid was added to aromatic polycarbonate pomopolymer (molecular weight 25,000) made from 2-bis(4-hydroxyphenyl)propane (bisphenol A). As a potassium salt, in the above general formula, N6 and N8 are chlorine (manufactured by Sangen Kagaku@, product name: PP-57)
, Xs is bromine and N8 is chlorine (manufactured by Sangen Kagaku@, product name: PP-67), N6 and N8 are bromine (manufactured by Sangen Kagaku ■, product name: PP-35), N3 is Bromine with N6 and χB being chlorine (manufactured by Sangen Kagaku ■, product name:
PP-61),
X61, N8 is chlorine (manufactured by Sangen Kagaku@, product name: P
P-62), as an aromatic phosphite compound,
Triphenylbosphite (manufactured by Johoku Kagaku Okiku, product name:
Jl) 360), diphenyl monodecyl phosphite (Johoku Kagaku 91M, trade name: JPM311),
Hydrogenated bisphenol A bosphite polymer (manufactured by Johoku Kagaku Co., Ltd., trade name: IIBP, molecular weight 2,400-3
,000), and as an organic silicon compound, methyltrinonyloxirane (manufactured by Ohe Kagaku@, trade name:
5l-49), tetradodecyl silicate (Oihe Chemical @
(trade name: 5r-413) were added and mixed in the proportions shown in Table 1, and the mixture was melted and kneaded in an extruder with a cylinder temperature of 250°C to form pellets. The pellets were injection molded into flame test specimens (5-inch x each inch x 1/16 inch thick).
-inch) test pieces were molded.

Using this test piece, Llinderwriters in the United States
'Laboratoris+ Inc, 5tand
ard for Flammability of Pl
astic Materials for Parts
in Devices and Appliances
, was tested based on the test method described in UL 94.

According to this tlL 94 test method, five test pieces are
Based on the results, 94V-0,
They are spelled as 94V-1, 94V-2, etc. The criteria are: -94V-0--The average time of complete explosion and/or glow after removing the ignition flame must not exceed 5 seconds. And none of the specimens should drop any fully exploding particles that would ignite the cotton wool.

-94V-1--The average time of complete explosion and/or glow after removal of the ignition flame shall not exceed 25 seconds. And none of the specimens should drop any fully exploding particles that would ignite the cotton wool.

-94V-2--The average time of complete dissolution and/or glow after removal of the ignition flame shall not exceed 25 seconds. The test piece may then drop a fully exploded particle that ignites the cotton wool.

In addition, a test piece that continues to burn for 25 seconds or more after the ignition flame is removed is not classified by 94V, and is considered to be rejected by this invention.
are categorized.

The results are shown in Table 1.

In addition, a melting test was conducted on the blended molding material to test for a decrease in molecular weight.

The evaluation was performed by heating the sample at 300° C. for 1 hour in a N2 stream, and then determining the molecular weight by determining the solution viscosity by α1. The molecular weight after treatment is shown as after testing.

For comparison, homopolymer alone (Comparative Example-1), compositions excluding the aromatic phosphite compound and organosilicon compound in the compositions of 2 Examples-1 to 6 (Comparative Examples-2 and 3)
The results were also shown in Table 1 in the same manner as in the examples.

Examples 7 to 9 and Comparative Examples 4 and 5 Polycarbonate resin made from bisphenol A (
(molecular weight 30,000), the same organophosphate potassium salt CP'P-57, PP-3 as used in Examples-1 to 6
5) Aromatic phosphite compound (IIBP)
, and an organic silicon compound (SI-413) as a second
They were added and mixed in the proportions shown in the table, and pelletized in the same manner as Examples 1 to 6.

Using this pellet, a C3A flame retardant standard test piece 101.6 x 152.4 fin x 2.2-3°2 x 2 (thickness) was molded by injection molding.

Using this test piece, Canadian Sta.
ndards As5ocation+ Elect
rical BulletinNa96B, CIaus
Tested based on the test method described in 6.11 Frame.

According to this test method, a burner with a test flame controlled to have an internal blue flame of 1z inch length and a total length of 5 inches is attached to the test piece, and the tip of the internal blue flame reaches the test piece at about 20 degrees. Apply it 5 times for 15 seconds, touching the center of the
Pass/fail is evaluated based on burning time and the opening status of the test piece.

The evaluation criteria according to the C3A flame retardant standard are as follows.

・A- Burning time: After the first four ignitions, extinguish the fire within 30 seconds each time. After the fifth and final ignition, extinguish the fire within one minute.

-B-Aperture: The hole opened in the test piece must not be large enough to allow a 2 inch φ test rod to pass through.

The results are shown in Table 1.

For comparison, homopolymer alone (Comparative Example-4), Example-
Table 2 also shows the results of a composition obtained by removing the aromatic phosphite compound and the organosilicon compound in the composition of No. 9 (Comparative Example-5) in the same manner as in the Example.

Tejuku, IT i9. True, written (spontaneous) January 22, 1985 Patent Application No. 004638 of 1988 2, Name of the invention Flame-retardant polycarbonate resin composition 3, Relationship with the case of the person making the amendment (patent applicant) Address (■100) 2-5-2 Marunouchi, Chiyoda-ku, Tokyo Name <44.6) Mitsubishi Gas Chemical Co., Ltd. Representative Kazuyoshi Nagano 4, Agent Address (■100) 2-5 Marunouchi, 1F, 1-ku, Chiyo, Tokyo 2.5, column 6 of ``Detailed explanation of the invention'' in the specification subject to amendment, and column ``Detailed explanation of the invention'' of the description of contents of the amendment, as follows.

■Render writer on the 4th line from directly below the 5th line
s Correct J to rUnderwriters' J @■ Correct "Flame retardant value" in "Page 6, Line 5 l" to "Flame retardant".

■Correct "Usage ga" in the second line of page 10 to "Usage ga".

■ Correct "methyltrinonyloxirane" on page 16, line 13 to "methyltrinonyloxirane".

■Correct "Table 2" in line 10 of page 21 to "Table 2."

I”d

Claims (1)

[Scope of Claims] To 100 parts by weight of an aromatic polycarbonate resin made from an aromatic dihydroxydiphenylalkane that does not contain a halogenated aromatic dihydroxydiphenylalkane component, Ta) an organic potassium phosphate salt represented by the following general formula (1). 0.001 to 5.0 parts by weight (bl aromatic arsenite compound 0.001 to 0
．． 5 parts by weight, and (0 to 0.5 parts by weight of a C1 organosilicon compound). Aryl group, or G substituted with halogen-
)