JPH09310013A - Flame-retardant polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant polycarbonate resin composition which is excellent in heat stability with reduced change in color tone of the resin, while it stays. SOLUTION: To 100 pts.wt. of a polycarbonate thermoplastic resin comprising (a) 50-99wt.% of an aromatic polycarbonate resin and (b) 1-50wt.% of halogenated aromatic polycarbonate, are formulated (C) 0.01-5 pts.wt. of a metal sulfonate salt, (d) 0.01-0.5 pt.wt. of an organic phosphite and (e) 0.01-0.5 pt.wt. of an organosilane whereby the objective polycarbonate resin composition is obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant polycarbonate resin composition, and more particularly to a flame-retardant polycarbonate resin composition having a significantly improved thermal stability during retention.

[0002]

2. Description of the Related Art Conventionally, it has been considered to add an alkali metal salt of sulfonic acid, a halogen-based polymer compound, a halogen-based compound, a halogenated aromatic polycarbonate, etc. to a flame-retardant aromatic polycarbonate resin. There is. However, a material containing a halogenated compound, a halogenated polymer compound or a sulfonic acid metal salt has a low thermal stability and is particularly susceptible to thermal discoloration, and even if a phosphite stabilizer or a phenol stabilizer is added. The improvement effect is poor, and there is a problem that a burning problem occurs in large-scale molding in the electric and electronic fields.

Further, when a halogenated aromatic polycarbonate is used, since the halogen group content in the halogenated aromatic polycarbonate is relatively low, the combustibility is not sufficiently satisfactory, and the halogenated aromatic polycarbonate is not sufficiently satisfied. When a halogenated aromatic carbonate oligomer, which is a low molecular weight substance of polycarbonate, is used, there is a problem in that the amount of the oligomer added tends to increase and the physical properties and thermal stability tend to deteriorate. Further, although improvement of flame retardancy by using a halogenated aromatic polycarbonate and a metal salt of sulfonic acid in combination has been investigated, the hue change during retention is large, and this is a problem especially in molding of large-sized molded products or thin-walled molded products. was there.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a flame-retardant polycarbonate resin composition having a small change in hue during retention and excellent thermal stability.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problem, and its gist is as follows:
50-99% by weight of aromatic polycarbonate resin (b)
100 parts by weight of a polycarbonate-based thermoplastic resin composed of 1 to 50% by weight of a halogenated aromatic polycarbonate, 0.01 to 5 parts by weight of (c) a sulfonic acid metal salt,
The flame-retardant polycarbonate resin composition comprises (d) an organic phosphite compound in an amount of 0.01 to 0.5 part by weight and (e) an organic silane compound in an amount of 0.01 to 0.5 parts by weight.

Hereinafter, the present invention will be described in detail. As the aromatic polycarbonate resin (a) in the present invention, an aromatic hydroxy compound or a small amount of a polyhydroxy compound and an optionally branched thermoplastic aromatic polycarbonate resin produced by reacting the compound with phosgene or a carbonic acid diester may be used. It is a union or a copolymer.

The aromatic dihydroxy compound is 2,
2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, tetrabromobisphenol A, bis (4-hydroxyphenyl) -P-diisopropylbenzene, hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, etc. And bisphenol A is preferable.

To obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2,4,4
6-tri (4-hydroxyphenyl) heptene-2,
4,6-Dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-
Tri (4-hydroxyphenylheptene-3,1,3,3
5-tri (4-hydroxyphenyl) benzene, 1,
A polyhydroxy compound represented by 1,1-tri (4-hydroxyphenyl) ethane or the like, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin, 5,7-
Dichloroisatin, 5-bromoisatin, etc. may be used as a part of the aromatic dihydroxy compound, and the amount used is 0.01 to 10 mol%, preferably 0.1.
~ 2 mol%.

To control the molecular weight, a monovalent aromatic hydroxy compound may be used, and m- and p-methylphenol, m- and p-propylphenol, p-bromophenol, p-tert-butylphenol and p- Examples include long-chain alkyl-substituted phenols. The aromatic polycarbonate resin is preferably a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or derived from 2,2-bis (4-hydroxyphenyl) propane and another aromatic dihydroxy compound. The polycarbonate copolymer is used. As the aromatic polycarbonate resin, two or more kinds of resins may be mixed and used.

The molecular weight of the aromatic polycarbonate resin is
Using methylene chloride as a solvent, the viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. is 1
6,000 to 30,000, preferably 18,000 to
28,000.

Examples of the (b) halogenated aromatic polycarbonate in the present invention include homopolymers, copolymers and oligomers obtained from tetrabromobisphenol-A as a raw material by a conventional method, and are represented by the following formula (4). It is a brominated aromatic polycarbonate having a repeating unit.

Embedded image

In the formula (4), m is an integer of 2 to 100, preferably 2 to 50, more preferably 2 to 20. The halogenated aromatic polycarbonate is preferably a brominated aromatic carbonate oligomer or the like. By using a brominated aromatic carbonate oligomer, it is possible to increase the content of bromine, and thus in terms of flame retardance,
It is also preferable in terms of moldability. The ends of the halogenated aromatic polycarbonate may be terminated with a halogen-containing end cap.

The polycarbonate type thermoplastic resin in the present invention includes (a) aromatic polycarbonate resin 5
0 to 99 wt% and (b) 1 to 50 wt% halogenated aromatic polycarbonate. When the amount of the halogenated aromatic polycarbonate is less than 1% by weight, sufficient flame retardancy cannot be obtained, and when it exceeds 50 parts by weight, physical properties such as impact strength tend to be deteriorated. The polycarbonate-based thermoplastic resin is preferably an aromatic polycarbonate resin 95 to 8
0% by weight and (b) halogenated aromatic polycarbonate 5
-20% by weight. As the polycarbonate-based thermoplastic resin, in addition to aromatic polycarbonate resin and halogenated aromatic polycarbonate, 40% by weight of thermoplastic resin such as polyester resin such as polybutylene terephthalate and polyethylene terephthalate, polyamide resin, ABS resin, polyolefin resin, etc. It may be contained below, preferably not more than 20% by weight.

Examples of the (c) sulfonic acid metal salt in the present invention include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts, and more specifically, aromatic sulfone sulfonic acid metal salts and perfluoroalkane-sulfone. Acid metal salts and the like, preferably aromatic sulfone sulfonic acid metal salts, perfluoroalkane-sulfonic acid metal salts and the like, and as the metal of the sulfonic acid metal salt, preferably,
Examples thereof include alkali metals and alkaline earth metals. Examples of the alkali metals and alkaline earth metals include sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium. As the aromatic sulfone sulfonic acid metal salt, preferably, an aromatic sulfone sulfonic acid alkali metal salt, an aromatic sulfone sulfonic acid alkaline earth metal salt and the like can be mentioned, and an aromatic sulfone sulfonic acid alkali metal salt, an aromatic sulfone sulfone The acid alkaline earth metal salt may be a polymer.

Specific examples of the metal salt of aromatic sulfone sulfonic acid include sodium salt of diphenyl sulfone-3-sulfonic acid, potassium salt of diphenyl sulfone-3-sulfonic acid, and 4,4'-dibromodiphenyl-sulfone-3.
-Sodium salt of sulfone, potassium salt of 4,4'-dibromodiphenyl-sulfone-3-sulfone, calcium salt of 4-chloro-4'-nitrodiphenylsulfone-3-sulfonic acid, diphenylsulfone-3,3'-disulfone Acid disodium salt, diphenyl sulfone-3
Examples thereof include dipotassium salt of 3'-disulfonic acid.

The perfluoroalkane-sulfonic acid metal salt is preferably an alkali metal salt of perfluoroalkane-sulfonic acid, an alkaline earth metal salt of perfluoroalkane-sulfonic acid, or the like, more preferably having a carbon number. Examples thereof include a sulfonic acid alkali metal salt having a 4 to 8 perfluoroalkane group, and a sulfonic acid alkaline earth metal salt having a C 4 to 8 perfluoroalkane group. Specific examples of perfluoroalkane-sulfonic acid metal salts include perfluorobutane-sodium sulfonate, perfluorobutane-potassium sulfonate,
Sodium perfluoromethylbutane-sulfonate, potassium perfluoromethylbutane-sulfonate, sodium perfluorooctane-sulfonate, potassium perfluorooctane-sulfonate, perfluorobutane-
Examples thereof include tetraethylammonium salt of sulfonic acid.

The sulfonic acid metal salts may be used as a mixture of two or more kinds. The compounding amount of sulfonic acid metal salt is
It is 0.01 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic polycarbonate resin. If the amount is less than 0.01 parts by weight, sufficient flame retardancy is difficult to obtain, and if the amount exceeds 5 parts by weight, the thermal stability tends to decrease. The compounding amount of sulfonic acid metal salt is
For 100 parts by weight of the thermoplastic polycarbonate resin,
Preferably 0.01 to 4 parts by weight, more preferably 0.0.
2-3 parts by weight.

As the organic phosphite compound (d) in the present invention, a phosphite compound which is usually used as an antioxidant of a polycarbonate resin can be used. For example, it is a dialkyl ester of pentaerythritol diphosphite. Examples thereof include an organic phosphite compound represented by the following formula (2) and an organic phosphite compound represented by the following formula (3) which is an ester of phosphorous acid and phenols.

[0019]

[Chemical 6]

In the formula (2), R ⁴ is a C3-21 aliphatic hydrocarbon group or aromatic hydrocarbon group, preferably a group represented by the following formula (5).

[0021]

[Chemical 7]

In the formula (5), R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom or a C1-5 alkyl group.

[0023]

Embedded image

In the formula (3), R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom or a C1-5 alkyl group. Examples of the organic phosphite compound represented by the formula (2) include 2,6-di-t-butyl-4-methylphenyl.
Phenyl pentaerythritol diphosphite, 2,6
-Di-t-butyl-4-methylphenyl isooctyl pentaerythritol diphosphite, bis (2,6-
Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-) Butylphenyl) pentaerythritol diphosphite and the like, and specific products include “Adeka Stab PEP-24G, Asahi Denka Kogyo KK”, “Adeka Stab PEP-36, Asahi Denka Kogyo KK”, etc. To be

Examples of the organic phosphite compound represented by the formula (3) include triphenyl phosphite, tris (nonylphenyl) phosphite, phenyldi (nonylphenyl) phosphite and tris (2,4-di-t).
-Butylphenyl) phosphite and the like, and specific products include "ADEKA STAB 2112, Asahi Denka Kogyo Co., Ltd." and the like. The compounding amount of the organic phosphite compound is 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the thermoplastic polycarbonate resin. If it is less than 0.01 part by weight, the change in hue during retention tends to be large,
If it exceeds 0.5 parts by weight, it tends to cause gas during molding. The content of the organic phosphite compound is preferably 100 parts by weight of the polycarbonate-based thermoplastic resin,
0.02-0.4 parts by weight, more preferably 0.03-
0.2 parts by weight.

As the (e) organosilane compound in the present invention, a silicon compound having an alkoxy group, a vinyl group,
Examples thereof include a silicon compound having a reactive functional group such as an acrylic group, a methacrylic group, an epoxy group, and an amino group, a silicon compound having a non-reactive group such as a phenyl group, and an alkoxysilane. Silane agents used for surface modification of inorganic substances and resin modifiers, or vinylsilane, acrylic silane, epoxy silane, etc. which are used as coupling agents such as fillers, A compound represented by the following formula (1) is preferable.

[0027]

Embedded image (R ¹ O) _n Si (R ² ) (R ³ ) _(3-n) (1)

In the formula, R ¹ is a methyl group, an ethyl group, a methoxyethyl group, a methoxymethyl group, an ethoxyethyl group or an ethoxymethyl group, and R ² is a C6-12 aromatic or alicyclic hydrocarbon. Group, C3-12 aliphatic hydrocarbon group, C2-16 ethylenically unsaturated hydrocarbon group,
Or an organic group having a C3-15 epoxy group,
Preferably, a C6-12 aromatic hydrocarbon group, C2-1
6 is an organic group having an ethylenically unsaturated hydrocarbon group of 6 or a C3-15 epoxy group, R ³ is a methyl group or an ethyl group, and n is 2 or 3.

Examples of the C6-12 aromatic or alicyclic hydrocarbon group include a phenyl group and a cyclohexyl group, and examples of the C3-12 aliphatic hydrocarbon group include a propyl group, a butyl group and an isobutyl group. Examples of the C2-16 ethylenically unsaturated hydrocarbon group include a vinyl group, an allyl group, an isopropenyl group, a butenyl group, a methacryloxypropyl group, and an acrylooxypropyl group. Examples of the organic group having an epoxy group of to 15 include 3,4 epoxycyclohexyl group and glycidoxypropyl group.

Specific examples of the organic silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane and β- (3.
4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, γ-
Examples thereof include glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and phenyltrimethoxysilane. The organosilane compound is
They can be used alone or as a mixture.

The compounding amount of the organosilane compound is 0.01 to 100 parts by weight of the thermoplastic polycarbonate resin.
0.5 parts by weight. If it is less than 0.01 part by weight, the effect of improving the hue change is small, and if it exceeds 0.5 part by weight, it is likely to cause gas during molding. The compounding amount of the organic silane compound is preferably 0.02 to 0.4 part by weight, and more preferably 0.02 to 0.2 part by weight, based on 100 parts by weight of the polycarbonate-based thermoplastic resin. In the flame-retardant polycarbonate resin composition of the present invention, a polycarbonate-based thermoplastic resin, a sulfonic acid metal salt, an organic phosphite compound and an organic silane compound, by blending each in a specific amount, excellent flame retardancy and remarkable Hue improvement is achieved.

The method for producing the flame-retardant polycarbonate resin composition of the present invention is not particularly limited, and for example, an aromatic polycarbonate resin, a halogenated polycarbonate, a sulfonic acid metal salt, an organic phosphite compound and an organic silane compound can be collectively used. Method of melt-kneading, aromatic polycarbonate resin and sulfonic acid metal salt, and aromatic polycarbonate resin and organic silane compound after previously kneading, or aromatic polycarbonate resin, sulfonic acid metal salt and organic silane compound after previously kneading, halogen A method of blending the compounded polycarbonate and the organic phosphite compound and melt-kneading, and the like can be mentioned. The flame-retardant polycarbonate resin composition of the present invention, if necessary,
UV absorbers, stabilizers such as antioxidants, pigments, dyes, lubricants, flame retardants, release agents, additives such as slidability improvers, glass fibers, glass flakes, reinforcing agents such as carbon fibers, or titanic acid. Whiskers such as potassium and aluminum borate can be added and blended.

[0033]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

The following raw materials were used in Examples and Comparative Examples. (1) Polycarbonate resin (Upilon S-200
0, manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 23,000, poly-4,4-isopropylidenediphenyl carbonate.
(2) Brominated carbonate oligomer (Iupilon F
R-53 manufactured by Mitsubishi Gas Chemical Co., Ltd. (3) Sulfonic acid metal salt a (potassium perfluoroalkanesulfonic acid, Megafac F114, manufactured by Dainippon Ink and Chemicals, Inc., chemical formula C ₄ F ₇ SO ₃ K) (4) Sulfonic acid metal salt b (diphenylsulfonesulfonic acid potassium salt, KSS, UCB Japan Ltd.)

(5) Phosphite compound a (Adeka Stab 2112, tris (2,4-di-t-butylphenyl) phosphite, manufactured by Asahi Denka Co., Ltd.) (6) Phosphite compound b (Adeka Stub PEP-3)
6, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, manufactured by Asahi Denka Co., Ltd. (7) Organosilane compound a (KBM303, β (3,4)
Epoxycyclohexyl) ethyltrimethoxysilane,
(8) Organosilane compound b (KBM103, phenyltrimethoxysilane, manufactured by Shin-Etsu Silicon Co., Ltd.) (9) Organosilane compound c (KBM503, γ (methacryloxypropyl) trimethoxysilane, Shin-Etsu Silicon Co., Ltd. (10) Organosilane compound d (KBM403, γ-glycidoxypropyltrimethoxysilane, Shin-Etsu Silicon Co., Ltd.) (11) Organosilane compound e (KBE402 γ-glycidoxypropylmethyldiethoxy) Silane, manufactured by Shin-Etsu Silicon Co., Ltd.

The physical properties of the test pieces were evaluated as described below. (1) Retention molded product Hue: 3 mm, 2 mm, 1 mm thick three-stage plate was used, and hue change in 3 mm portion was evaluated using a color computer of Suga Test Instruments Co., Ltd. 1 shot The hue difference between the eye and the 10th shot is represented by ΔE, and the difference in the yellow index is represented by ΔYI. In each case, the smaller the value, the smaller the change in hue and the better. (2) Flammability: A vertical flammability test was conducted using a 1.6 mm thick UL standard test piece for evaluation.

Example 1 85 parts by weight of a polycarbonate resin and 15 parts by weight of a brominated carbonate oligomer were added with 0.05 part by weight of a sulfonic acid metal salt a, 0.1 part by weight of a phosphite compound a, and 0.05 part by weight of an organic silane compound a. After mixing and mixing for 20 minutes with a tumbler, pelletize at a cylinder temperature of 270 ° C with a 40 mm single-screw extruder, form a 1.6 mm thick combustion test piece with an injection molding machine, and UL
Evaluation was made according to the test method. Further, a three-stage plate was molded at a cylinder temperature of 300 ° C. for a cooling time of 180 seconds, the hue of each shot was evaluated by a color computer of a Suga Tester, and the color difference between the first shot and the tenth shot was measured. . The results are shown in Table 1.

Example 2 Pelletization was carried out in the same manner as in Example 1 except that sulfonic acid a was changed to sulfonic acid b, and the same evaluation was carried out. Table 1 shows the results.
Shown in Example 3 In Example 1, the phosphite compound a
Was pelletized by the same method as in Example 1 except that was changed to phosphite compound b, and the same evaluation was performed. The results are shown in Table 1. Example 4 Pelletization was performed in the same manner as in Example 1 except that the organosilane compound a was changed to the organosilane compound b, and the same evaluation was performed. Table 1 shows the results.
Shown in [Example 5] Pelletization was performed in the same manner as in Example 1 except that the organosilane compound a was changed to the organosilane compound c, and the same evaluation was performed. Table 1 shows the results.
Shown in [Example 6] Pelletization was performed in the same manner as in Example 1 except that the organosilane compound a was changed to the organosilane compound d, and the same evaluation was performed. Table 1 shows the results.
Shown in [Example 7] Pelletization was performed in the same manner as in Example 1 except that the organosilane compound a was changed to the organosilane compound e, and the same evaluation was performed. Table 1 shows the results.
Shown in

[0039]

[Table 1]

Comparative Example 1 Pelletization was carried out in the same manner as in Example 1 except that the organosilane compound a and the phosphite compound a were not used, and the same evaluation was performed. Table 2 shows the results. Comparative Example 2 Pelletization was carried out in the same manner as in Example 2 except that the organosilane compound a and the phosphite compound a were not used, and the same evaluation was performed. Table 2 shows the results. [Comparative Example 3] Pelletization was carried out in the same manner as in Example 1 except that the organosilane compound a was not used,
Evaluation was performed similarly. Table 2 shows the results. [Comparative Example 4] Pelletization was carried out in the same manner as in Example 2 except that the organosilane compound a was not used.
Evaluation was performed similarly. Table 2 shows the results. [Comparative Example 5] Pelletization was carried out in the same manner as in Example 3 except that the organosilane compound a was not used.
Evaluation was performed similarly. Table 2 shows the results. [Comparative Example 6] In Example 1, the phosphite compound a was used.
Pelletization was carried out in the same manner as in Example 1 except that was not used, and the same evaluation was performed. Table 2 shows the results.

[0041]

[Table 2]

[0042]

EFFECTS OF THE INVENTION The flame-retardant polycarbonate resin composition of the present invention has excellent flame retardancy, a small change in hue during retention, and excellent thermal stability. It is useful as a large-sized molded product or a thin-walled molded product.

Claims (6)

[Claims] 1. (a) Aromatic polycarbonate resin 50
To 99% by weight and (b) 1 to 50% by weight of a halogenated aromatic polycarbonate in 100 parts by weight of a thermoplastic polycarbonate resin, (c) a sulfonic acid metal salt of 0.0
1 to 5 parts by weight, (d) organic phosphite compound 0.01
To 0.5 parts by weight and (e) an organosilane compound 0.01
A flame-retardant polycarbonate resin composition containing 0.5 to 0.5 parts by weight. 2. The flame-retardant polycarbonate resin composition according to claim 1, wherein the organosilane compound is an organosilane compound represented by the following formula (1). Embedded image (R ¹ O) _n Si (R ² ) (R ³ ) _(3-n) (1) (In the formula (1), R ¹ is a methyl group, an ethyl group, a methoxyethyl group, or a methoxymethyl group. Group, an ethoxyethyl group or an ethoxymethyl group, R ² is a C6-12 aromatic or alicyclic hydrocarbon group, a C3-12 aliphatic hydrocarbon group, a C2-16 ethylenically unsaturated hydrocarbon group. Group or an organic group having a C3-15 epoxy group, R ³ is a methyl group or an ethyl group, and n is 2 or 3.) 3. The flame-retardant polycarbonate resin composition according to claim 1, wherein the sulfonic acid metal salt is an sulfonic acid alkali metal salt or a sulfonic acid alkaline earth metal salt. 4. The flame-retardant polycarbonate resin according to any one of claims 1 to 3, wherein the sulfonic acid metal salt is an aromatic sulfone sulfonic acid metal salt or a perfluoroalkane-sulfonic acid metal salt. Composition. 5. The flame-retardant polycarbonate resin according to any one of claims 1 to 4, wherein the organic phosphite compound is an organic phosphite compound represented by the following formula (2) or (3). Composition. Embedded image (In the formula (2), R ⁴ represents a C3-21 aliphatic hydrocarbon group or aromatic hydrocarbon group.) (In the formula (3), R ⁵ , R ⁶ , and R ⁷ are each a hydrogen atom or a C1-5 alkyl group.) 6. A halogenated aromatic polycarbonate is
The flame-retardant polycarbonate resin composition according to any one of claims 1 to 5, which is a brominated aromatic polycarbonate having a repeating unit represented by the formula (4). Embedded image (In the formula (4), m is an integer of 2 to 100.)