JPS626588B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION The present invention relates to flame retardant polycarbonate resin compositions. More specifically, the flame retardant has been improved by adding a small amount of sulfuric ester metal salts of monohydric and/or polyhydric alcohols and fluorinated polyolefins to provide resistance even when exposed to severe flames. The present invention relates to a polycarbonate resin composition. Many methods are known for making polycarbonate flame retardant. Most of these methods involve adding a relatively large amount of an organic halogen compound, but this method significantly deteriorates the polycarbonate and causes a significant drop in impact resistance. As a result of intensive research to find a flame-retardant polycarbonate resin composition that does not melt and drip even when exposed to severe flames and maintains impact resistance, the inventors have found that aromatic By adding a small amount of sulfuric acid ester metal salts of monohydric and/or polyhydric alcohols and fluorinated polyolefins to polycarbonate, the mutual effect of the two makes flame retardant without impairing impact resistance. The present invention was completed after discovering the surprising fact that the effect is significantly improved. That is, the present invention provides: 1. A flame-retardant polycarbonate resin composition prepared by adding sulfuric acid ester metal salts of monohydric and/or polyhydric alcohols and fluorinated polyolefins to aromatic polycarbonate. 2 As sulfuric ester metal salts of monohydric and/or polyhydric alcohols, alcohols include halogen-substituted and/or unsubstituted alkyl alcohols having 1 to 40 carbon atoms, cycloalkyl alcohols, aralkyl alcohols, glycols,
The alcohol is selected from the group consisting of glycerol and pentaerythritol, and the metal salt is a metal salt selected from the group consisting of alkali metal salts and/or alkaline earth metal salts and mixtures of these salts. Range 1
Compositions as described in Section. 3. The composition according to claim 1, wherein the fluorinated polyolefin is polytetrafluoroethylene. 4. The composition according to claim 1, wherein the fluorinated polyolefin is an ethylene-tetrafluoroethylene copolymer. It is. 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. Divalent phenol compounds other than bisphenol A include, for example, hydroquinone, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)alkane, bis(4-hydroxyphenyl)
Cycloalkane, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl)
These are compounds such as ether, bis(4-hydroxyphenyl)ketone, or halogen-substituted products thereof. It may be a homopolymer of these dihydric phenols, a copolymer of two or more types, or a blend thereof. The sulfuric acid ether salts used in the present invention are alkali metal or alkaline earth metal salts of monohydric and/or polyhydric alcohol sulfuric esters, such as methyl sodium sulfate, ethyl sodium sulfate, lauryl sodium sulfate, hexadecyl Sodium sulfate, potassium methyl sulfate, potassium ethyl sulfate,
Potassium lauryl sulfate, potassium hexadecyl sulfate, sodium polyoxyethylene alkyl ether sulfate, potassium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, potassium polyoxyethylene alkyl phenyl ether sulfate, ethylene glycol monolaurate Sodium monosulfate, propylene glycol monostearate sodium monosulfate, pentaerythritol mono, di, tri, and tetrasulfate sodium, laurate monoglyceride monosulfate, palmitic acid monoglyceride monosulfate, stearate monoglyceride monosulfate, 1 - 3-Bis(2-ethylhexyl)glycerin ether Sodium monosulfate, soda salt of sulfated phenoxy resin, etc. may be mentioned, but halogen-substituted products of these may also be used. These compounds may be used alone or in combination of two or more. The amount of these sulfate ester salts added is, for example, 0.001 to
It is used by adding 2% by weight. Particularly preferably,
It is 0.005-0.5% by weight. The fluorinated polyolefin used in the present invention is
Polymers of fluorine compounds of olefins such as ethylene, propylene, etc., such as polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, polytrifluorochloroethylene, vinylidene fluoride, ethylene-tetrafluoroethylene An ethylene copolymer etc.,
For polycarbonate resin compositions, e.g.
It is used by adding 0.1 to 10% by weight. As a method for adding these additives to the polycarbonate resin, a conventional blending method such as dry blending using a super mixer, tumbler, etc. is used. 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 or the like, and the pellets can be processed into various molded products by a conventional molding method. The composition may also contain conventional additives such as stabilizers, antioxidants, mold release agents, lubricants, fillers, reinforcing agents such as glass fibers, carbon fibers, blowing agents, dyes and pigments, antistatic agents, ultraviolet rays, etc. Additives such as absorbers, organic halogen compound flame retardants, or flame retardant aids such as antimony compounds can be added. As a method for evaluating flame retardancy, Subject 94 (UL) by Underwriters Laboratories, Inc.
-94), but when the composition of the present invention is evaluated according to this method, it shows a very remarkable flame retardant effect. The present invention will be specifically described below with reference to Examples. Examples 1 to 3 Sodium lauryl sulfate and polytetrafluoroethylene (trade name: Yunon P) were added to polycarbonate powder (average molecular weight 25,000) consisting of bisphenol A in the proportions shown in Table 1, and the mixture was heated at 500 °C for 10 minutes in a super mixer. After vigorously stirring at a rotation speed of 1 minute per minute, the mixture was extruded into pellets at 250 to 280°C using a vented 30 mmφ extruder. After drying this pellet at 120°C for 6 hours, it was molded into 127mm x 12.7mm x 3.2~6.4mm pellets using an injection molding machine.
mm, 127mm×127mm×3.2~6.4mm, and 64mm×
It was injection molded into a 12.7 mm x 3.2 mm test piece. Flammability evaluation is UL-94, impact resistance evaluation is JIS
K-6719 was followed. The IX-94 test includes
There are ratings such as HB, V-2, V-1, V-0, and 5V, but the 5V test is the most severe and difficult to pass.
This 5V test consists of a set of 5 bar samples and a plaque sample, and the grading criteria are roughly as follows. Bar sample test method: Light the burner and adjust the flame to an outer flame of 127 mm and an inner flame of 38 mm.
Then, tilt the burner at an angle of 20 degrees to the vertical, and repeat 5 seconds of flame contact and 5 seconds of flame extinguishment 5 times so that the tip of the inner flame touches the lower end of the vertically hung test specimen, and the flame does not burn for more than 60 seconds. , and no drippings are the criteria for passing. Plaque sample test method Using a similar burner, apply the flame downward for 5 seconds to the bottom corner, bottom edge, center of one side, and horizontal surface of a plaque hung vertically for 5 seconds. The criterion for passing is that the flame does not burn for more than 60 seconds after extinguishing the flame 5 times, and that there is no dripping or significant damage. Examples 4-6 The polycarbonate powder used in Examples 1-3 was added with sodium hexadecyl sulfate and ethylene-
Example 1 A tetrafluoroethylene copolymer (trade name Afron COP) was added in the proportions shown in Table 1.
It was injection molded and evaluated in the same manner as in 3. Examples 7 to 9 Potassium stearyl sulfate and polytrifluorochloroethylene (trade name: Daiflon) were added to the polycarbonate powder used in Examples 1 to 3 in the proportions shown in Table 1, and injection was carried out in the same manner as in Examples 1 to 3. It was molded and evaluated. Comparative Example 1 The polycarbonate powder used in the example was pelletized according to the method of the example, injection molded in the same manner, and evaluated. Comparative Example 2 Polytetrafluoroethylene (trade name: Yunon P) was added to the polycarbonate powder used in the example in the proportions shown in Table 1, pelletized according to the method of the example, injection molded in the same manner, and evaluated. Comparative Examples 3 to 5 The polycarbonate powder used in the examples was
Sodium lauryl sulfate, sodium hexadecyl sulfate,
Potassium stearyl sulfate was added in the proportions shown in Table 1, and injection molding was carried out in the same manner as in the examples for evaluation.

【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 flame-retardant polycarbonate resin composition prepared by adding sulfuric acid ester metal salts of monohydric and/or polyhydric alcohols and fluorinated polyolefins to aromatic polycarbonate. 2 As sulfuric acid ester metal salts of monohydric and/or polyhydric alcohols, alcohols include halogen-substituted and/or unsubstituted alkyl alcohols having 1 to 40 carbon atoms, cycloalkyl alcohols, aralkyl alcohols, glycols, glycerol, pentyl alcohols, etc. Claim 1, wherein the alcohol is selected from the group consisting of erythritol, and the metal salt is a metal salt selected from the group consisting of alkali metal salts and/or alkaline earth metal salts and mixtures of these salts. Compositions as described. 3. The composition according to claim 1, wherein the fluorinated polyolefin is polytetrafluoroethylene. 4. The composition according to claim 1, wherein the fluorinated polyolefin is an ethylene-tetrafluoroethylene copolymer.