JPH0116435B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a flame-retardant polycarbonate resin composition. More specifically, a small amount of vinylidene fluoride-propylene fluoride-tetrafluoroethylene terpolymer and/or tetrafluoroethylene-
A flame-retardant polycarbonate resin that has been improved by adding a perfluoroalkyl vinyl ether copolymer and a small amount of a specific flame-retardant compound to prevent burning melt drippings even when exposed to flame for a relatively long period of time. Regarding the composition. [Prior Art] Many methods are known for making polycarbonate flame retardant. Among them, the method of adding a relatively large amount of an organic halogen compound has a large flame retardant effect, but it significantly deteriorates the polycarbonate and causes a significant decrease in impact resistance. In order to improve this drawback, flame retardant methods have been devised by adding small amounts of various organic alkali metal salts, but all of these can withstand relatively short flame exposure of about 10 seconds, but
The relatively long flame exposure of 120 seconds as described in the IEC standard SC50D was not always satisfactory. [Object of the Invention] The object of the present invention is to provide a flame retardant material that has excellent flame retardant properties that do not produce molten drippings even when exposed to flame for a relatively long time of 120 seconds, and that maintains impact resistance. The present invention provides a flammable polycarbonate resin composition. [Structure of the Invention] The present invention provides an aromatic polycarbonate resin containing a small amount of (A) unsubstituted or halogen-substituted carbon atoms having 6 to 6 carbon atoms.
Ethers derived from 40 monovalent or polyvalent phenols and a sulfoalkyl halide having 1 to 10 carbon atoms in which a sulfonic acid group is bonded to the carbon atom of the alkyl group: (B) The following general formula () [However, X in the formula is a halogen atom, and m is 0
or an integer from 1 to 4. Y is -R-SO ₃ M
(wherein R is an alkylene group having 1 to 10 carbon atoms, and M is an alkali metal or alkaline earth metal);
It is a hydrogen atom, an aliphatic group having 1 to 20 carbon atoms, or an aromatic group having 20 or less carbon atoms, and at least one of Y is a sulfoalkyl group represented by -R-SO ₃ M. Z is an alkylene group or alkylidene group having 1 to 9 carbon atoms, a cycloalkylene group or cycloalkylidene group having 5 to 15 carbon atoms, -O-, -S-, -SO-, -
SO ₂ −, −CO−, −CO ₂ −. n is 1 to 200
is the number of ] Polycarbonate having a sulfonic acid group at some or all of the terminals represented by: (C) The following general formula () R′(−COO−Y′) _n ………() [However, R′ is the number of carbon atoms 1 to 40 halogen-substituted and/or unsubstituted aliphatic or aromatic hydrocarbon groups, Y' is a hydrogen atom, -R''-SO ₃ M'(R'' is an alkylene group having 1 to 10 carbon atoms) can be,
M' is an alkali metal or alkaline earth metal), or an aliphatic or aromatic group having 1 to 20 carbon atoms, and at least one is -R''-
SO ₃ M', m is an integer from 1 to 6. ] Monovalent or polyhydric carboxylic acid esters represented by: (D) The alcohol component of the ester bond is a monohydric alcohol having 1 to 40 carbon atoms or a monohydric alcohol having 2 to 40 carbon atoms.
40 polyhydric alcohol sulfate ester salt: at least one flame retardant imparting compound selected from the group consisting of: and a small amount of vinylidene fluoride-propylene fluoride-tetrafluoroethylene terpolymer and/or tetrafluoro This is a flame-retardant polycarbonate resin composition containing an ethylene-perfluoroalkyl vinyl ether copolymer. The aromatic polycarbonate used in the present invention is produced by reacting dihydric phenol with phosgene or carbonic acid diester. As the divalent phenol compound, bisphenols are preferable, particularly 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A).
) is preferred. Further, part or all of bisphenol A may be replaced with another divalent phenol compound. Examples of divalent phenol compounds other than bisphenol A include hydroquinone, 4,4'-dihydroxyphenyl, and bis(4-hydroxyphenyl).
Alkane, bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) ) ether, bis(4-hydroxyphenyl)ketone, or halogen-substituted products thereof. Homopolymers of these divalent phenols, 2
It may be a copolymer of more than one species, a polymer having a branched structure, or a blend thereof. The vinylidene fluoride-propylene fluoride-tetrafluoroethylene terpolymer and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer used in the present invention can be used alone or in a mixed form, and are based on the total amount of the resin composition. ,
It is desirable to use it by adding 0.01 to 5% by weight. If the amount added is less than 0.01% by weight, combustion melt drips will occur, and if it exceeds 5% by weight, delamination will occur in the injection molded product, which is not preferable. The flame retardant imparting compound used in the present invention is disclosed in Japanese Patent Publication No. 56-26267, Japanese Patent Publication No. 56-26268, Japanese Patent Publication No. 56-26269, Japanese Patent Publication No. 56-26269,
Although the compound is disclosed in Publication No. 34180,
Particularly preferred compounds include sodium lauryl sulfate, sodium hexadecyl sulfate, sodium polyoxyethylene alkyl ether sulfate,
2,2-bis(4-γ-sodium sulfopropoxyphenyl)propane, 2,2-bis(4-β
-sodium sulfoethoxyphenyl)propane, 2,2-bis(3,5-dibromo-4-β-
sodium sulfoethoxyphenyl) propane,
2-(3,5-dibromo-4-β-sodium sulfoethoxyphenyl)-2-(3,5-dibromo-4-hydroxyphenyl)propane, bis(4
-β-sodium sulfoethoxyphenyl) sulfide, γ-sodium sulfopropoxy group-terminated poly[2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane carbonate] (average degree of polymerization = 3 to 5) , bis(γ-sodium sulfopropyl) phthalate, bis(γ-sodium sulfopropyl) tetrabromophthalate, mono(γ-sodium sulfopropyl) tetrabromophthalate, and potassium salts and calcium salts. It may be used in the form of a mixture of these. The amount of these compounds added is 0.001 to 2% by weight, preferably 0.005 to 1% by weight based on the total amount of the resin composition.
Add % by weight. If the amount added is less than 0.001% by weight, no flame retardant effect will be observed, and if the amount exceeds 2% by weight, the flame retardant effect will be saturated, so it is not necessary. Examples of the method for adding these additives to the polycarbonate resin include conventional blending methods such as dry blending using a super mixer, tumbler, or the like. The polycarbonate resin composition of the present invention can be molded into pellets or sheets by a conventional method using a vented extrusion molding machine, and the pellets can be processed into various molded products by a conventional molding method. The compositions of the present invention may also contain conventional additives such as stabilizers, antioxidants, mold release agents, lubricants, fillers, reinforcing agents such as glass fibers, carbon fibers,
Used by adding foaming agents, dyes and pigments, antistatic agents, ultraviolet absorbers, organic halogen compound flame retardants, flame retardant aids such as antimony compounds, fluorine-substituted and/or unsubstituted organic polysiloxane rubbers, etc. I don't mind if you do that. The evaluation of flame retardancy is based on the IEC standard SC50D, which is abbreviated below.
Compliant with. Needle Flame Test Using a burner with a length of 35 mm, an inner diameter of 0.5 ± 0.1 mm, and an outer diameter of 0.9 mm or less, adjust the flame to a length of 12 ± 2 mm using butane gas, and apply the flame to the test piece at a 45° angle.
The flame is set back for 120 seconds, and the combustion time is measured, and the presence or absence of drips burning the tissue paper on a white pine board placed 200±5 mm below the flame contact point is observed. Three test pieces are used, and (1) the test piece does not burn for more than 30 seconds. and (2) check that there are no combustion melted drippings that cause the tissue paper to catch fire, and if the above (1) and (2) are satisfied, the test is passed. [Example] Hereinafter, the present invention will be described in detail with reference to Examples. Examples 1 to 3 Two fluororubbers (DAIEL G501 manufactured by Daikin Industries, Ltd.) consisting of vinylidene fluoride-propylene fluoride-tetrafluoroethylene terpolymer were added to polycarbonate powder (average molecular weight 25,000) consisting of bisphenol A. - Cut into chips of about 3 mm,
Add the compounds shown in Table 1 together with the compounds shown in Table 1 in the proportions shown in Table 1, stir at 500 revolutions/minute for 2 minutes with a super mixer, and then use a 30 mmφ extruder with a vent at 250°C.
It was extruded at 280°C and pelletized. After drying the pellets at 120°C for 6 hours, they were molded into 127mm×
Test pieces of 12.7 mm x 1.6 mm and 64 mm x 12.7 mm x 3.2 mm were formed. Flammability was evaluated according to IEC standard SC50D, and impact resistance was evaluated according to JIS K-6719. Examples 4 to 6 Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (Neoflon PFA AP210 manufactured by Daikin Industries, Ltd.) was added to the polycarbonate powder used in Example 1 in the proportions shown in Table 1 together with the compounds shown in Table 1. , injection molded and evaluated in the same manner as in Example 1. Comparative Example 1 The polycarbonate powder used in Example 1 was pelletized according to the method of Example 1, injection molded in the same manner, and evaluated. Comparative Examples 2 to 3 The polycarbonate powder used in Example 1 was added with a fluorocarbon rubber consisting of vinylidene fluoride-propylene fluoride-tetrafluoroethylene terpolymer (Dai-el G501 manufactured by Daikin Industries, Ltd.), tetrafluoroethylene-par Fluoroalkyl vinyl ether copolymer (Neoflon PFA manufactured by Daikin Industries, Ltd.)
AP210) were added in the proportions shown in Table 1, injection molded and evaluated in the same manner as in Example 1. Comparative Examples 4 to 5 Sodium lauryl sulfate and bis(γ-sodium sulfopropyl tetrabromophthalate) were added to the polycarbonate powder used in Example 1 in the proportions shown in Table 1, and injection molded in the same manner as in Example 1. evaluated. Comparative Example 6 Polytetrafluoroethylene (Daikin Industries, Ltd.) was added to the polycarbonate powder used in Example 1.
1% of Leburon L-5) and 0.05% of sodium lauryl sulfate were added and injection molded in the same manner as in Example 1 and evaluated.

【table】

[Table] Molded articles made from the composition of the present invention exhibit excellent flame retardancy without impairing the excellent impact resistance of polycarbonate.

Claims (1)

[Scope of Claims] 1. A small amount of (A) unsubstituted or halogen-substituted carbon atoms having 6 to 6 carbon atoms in an aromatic polycarbonate resin.
Ethers derived from 40 monovalent or polyvalent phenols and a sulfoalkyl halide having 1 to 10 carbon atoms in which a sulfonic acid group is bonded to the carbon atom of the alkyl group: (B) The following general formula () [However, X in the formula is a halogen atom, and m is 0
or an integer from 1 to 4. Y is -R-SO ₃ M
(wherein R is an alkylene group having 1 to 10 carbon atoms, and M is an alkali metal or alkaline earth metal);
It is a hydrogen atom, an aliphatic group having 1 to 20 carbon atoms, or an aromatic group having 20 or less carbon atoms, and at least one of Y is a sulfoalkyl group represented by -R-SO ₃ M. Z is an alkylene group or alkylidene group having 1 to 9 carbon atoms, a cycloalkylene group or cycloalkylidene group having 5 to 15 carbon atoms, -O-, -S-, -SO-, -
SO ₂ −, −CO−, −CO ₂ −. n is 1 to 200
is the number of ] Polycarbonate having a sulfonic acid group at some or all of the terminals represented by: (C) The following general formula () R′(−COO−Y′) _n ………() [However, R′ is the number of carbon atoms 1 to 40 halogen-substituted and/or unsubstituted aliphatic or aromatic hydrocarbon groups, Y' is a hydrogen atom, -R''-SO ₃ M'(R'' is an alkylene group having 1 to 10 carbon atoms) can be,
M' is an alkali metal or alkaline earth metal), or an aliphatic or aromatic group having 1 to 20 carbon atoms, and at least one is -R''-
SO ₃ M', m is an integer from 1 to 6. ] Monovalent or polyhydric carboxylic acid esters represented by: (D) The alcohol component of the ester bond is a monohydric alcohol having 1 to 40 carbon atoms or a monohydric alcohol having 2 to 40 carbon atoms.
40 polyhydric alcohol sulfate ester salt: at least one flame retardant imparting compound selected from the group consisting of: and a small amount of vinylidene fluoride-propylene fluoride-tetrafluoroethylene terpolymer and/or tetrafluoro A flame-retardant polycarbonate resin composition comprising an ethylene-perfluoroalkyl vinyl ether copolymer. 2. The composition according to claim 1, wherein the salt in the ethers and sulfuric ester salts is an alkali metal salt or an alkaline earth metal salt. 3. The composition according to claim 1 or 2, wherein the amount of the flame retardant imparting compound added is 0.001 to 2% by weight based on the total amount of the composition. 4. The amount of vinylidene fluoride-propylene fluoride-tetrafluoroethylene terpolymer and/or tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer added is based on the total amount of the composition.
The composition according to claims 1 to 3, wherein the content is 0.01 to 5% by weight.