JPH0251938B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a flame-retardant resin composition. More specifically, the present invention has excellent moldability, durability, etc., and has excellent flame retardancy and mechanical strength, making it suitable as a material for housings and various parts of home appliances, OA equipment, etc. This invention relates to a flame-retardant resin composition. [Conventional technology] Polycarbonate resin, polyolefin resin,
Thermoplastic resins such as polystyrene, ABS resin, polyester, polyamide, acrylic resin, and polyvinyl chloride resin have various advantages such as good moldability, good durability, light weight, and low cost. Therefore, it has been applied to various fields, but on the other hand, it has the disadvantage of being easily flammable, so its fields of use are limited in some areas from the viewpoint of safety. Conventionally, in order to make thermoplastic resins flame retardant, flame retardants such as organic halides and phosphate esters have been added to thermoplastic resins, or metal oxides such as antimony trioxide have been added to these flame retardants. It is used as a flame retardant aid. Incidentally, in recent years, flame retardant standards such as the UL standard regarding the safety of thermoplastic resins have been strengthened year by year, so there is a strong demand for highly flame-retardant thermoplastic resins. Generally, thermoplastic resins can be made highly flame retardant by adding a large amount of flame retardant. Physical properties deteriorate significantly. In addition, there are various problems caused by thermal decomposition of flame retardants during melt molding, such as discoloration of resin,
Problems such as corrosion of machinery and working environment due to the generation of toxic corrosive gases also occur. Furthermore, there is a decline in the weather resistance of limited molded products, the generation of toxic gases during combustion,
There are also problems such as the toxicity of the flame retardant itself. [Problems to be Solved by the Invention] The purpose of the present invention is to improve the drawbacks of such conventional flame-retardant thermoplastic resins, and to create a flame-retardant resin with excellent flame retardancy and mechanical strength. An object of the present invention is to provide a resin composition. [Means for Solving the Problems] As a result of extensive research in order to develop a flame-retardant resin composition having such excellent characteristics, the present inventors found that a polycarbonate resin composed of an organic halogen compound By blending a small amount of polytetrafluoroethylene in addition to the flame retardant and flame retardant aid, it is possible to maintain the flame retardant effect while significantly reducing the amount of the flame retardant and flame retardant aid. Moreover, they found that the mechanical properties were not reduced, and based on this knowledge, they completed the present invention. That is, the present invention uses polycarbonate resin
It is characterized by containing 0.01 to 2 parts by weight of polytetrafluoroethylene, 0.1 to 30 parts by weight of a flame retardant made of an organic halogen compound, and 0.1 to 15 parts by weight of a flame retardant aid to 100 parts by weight. A flame retardant resin composition is provided. The polycarbonate resin used in the present invention is
There are no particular restrictions, and various types can be used. For example, by solvent method, i.e. in the presence of known acid acceptors, molecular weight modifiers in a solvent such as methylene chloride,
Typical polycarbonate resins are those obtained by the phosgene method, in which divalent phenol is reacted with a carbonate precursor such as phosgene, and the transesterification method, in which divalent phenol is reacted with a carbonate precursor, such as diphenyl carbonate. be. Dihydric phenols that can be suitably used here include bisphenols, particularly 22-bis(4-
Hydroxyphenyl)propane (hereinafter referred to as bisphenol A) is preferred, and bisphenol A may be partially or entirely replaced with other dihydric phenols. Bisphenol A
Other dihydric phenols include hydroquinone:4,4'-dihydroxydiphenyl:bis(4
-hydroxyphenyl) alkanes, e.g. 4,
4'-dihydroxy-diphenylmethane, 1,1-
Bis(4-hydroxyphenyl)ethane, 1,1
-bis(4-hydroxyphenyl)propane,
1,1-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-
2-methylpropane, 1,1-bis(4-hydroxyphenyl)heptane, 1,1-bis(4-hydroxyphenyl)-1-phenylmethane, 1,
1-bis(4-hydroxyphenyl)-(4-methylphenyl)methane, 1,1-bis(4-hydroxyphenyl)-(4-ethylphenyl)methane,
1,1-bis(4-hydroxyphenyl)-(4-
isopropylphenyl)methane, 1,1-bis(4-hydroxyphenyl)-(4-butylphenyl)methane, 1,1-bis(4-hydroxyphenyl)-benzylmethane, 2,2-bis(4- hydroxyphenyl)butane, 2,2-bis(4-
hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl) Octane, 2,2-bis(4-hydroxyphenyl)nonane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 3,3-bis(4-hydroxyphenyl)pentane, 4,4 −
Bis(4-hydroxyphenyl)heptane, 2,
2-bis(4-hydroxy-3-cyclohexylphenyl)propane, 2,2-(4,4'-dihydroxy-3-methyldiphenyl)propane, 2,
2-(4,4'-dihydroxy-3-isopropyldiphenyl)butane, 2,2-bis(4-hydroxy-3-butylphenyl)propane, 2,2-
Bis(4-hydroxy-3-phenyl)propane, 2,2-bis(4-hydroxy-2-methylphenyl)propane, 1,1-bis(4-hydroxy-3-methyl-6-butylphenyl)butane, 1, 1-bis(4-hydroxy-3-methyl-6-tert-butylphenyl)ethane, 1,1-
bis(4-hydroxy-3-methyl-6-tert-
butylphenyl)propane, 1,1-bis(4-
Hydroxy-3-methyl-6-tert-butylphenyl)butane, 1,1-bis(4-hydroxy-
3-Methyl-tert-butylphenyl)isobutane, 1,1-bis(4-hydroxy-3-methyl-6-tert-butylphenyl)heptane, 1,1
-bis(4-hydroxy-3-methyl-6-tert-butylphenyl)-1-phenylmethane, 1,
1-bis(4-hydroxy-3-methyl-6-tert-amylphenyl)butane etc.: bis(4-hydroxyphenyl)cycloalkane, e.g. 1,1
-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-
3-methylphenyl)cyclohexane, etc.: bis(4-hydroxyphenyl)sulfide, such as 4,4'-dihydroxydiphenylsulfide,
4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxy-3,
3'-diethyldiphenyl sulfide, 4,4'-dihydroxy-2,2'-dimethyldiphenyl sulfide, etc.: bis(4-hydroxyphenyl) sulfone, e.g. 4,4'-dihydroxydiphenyl sulfone , 4,4'-dihydroxy-2,2'-dimethyldiphenylsulfone, 4,4'-dihydroxy-
3,3'-dimethyldiphenylsulfone, 4,4'-
Dihydroxy-3,3',5,5'-tetramethyldiphenyl sulfone, etc.: bis(4-hydroxyphenyl) sulfoxide, such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-2,2 '-dimethyldiphenyl sulfoxide,
4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, etc.: bis(4-hydroxyphenyl) ether, such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,
3'-dimethyl diphenyl ether, 4,4'-dihydroxy-3,3'-diethyl diphenyl ether, 4,4'-dihydroxy-3,3'-dipropyl diphenyl ether, 4,4'-dihydroxy-
3,3'-diisopropylphenyl ether, 4,
4'-dihydroxy-2,2'-dimethyldiphenyl ether, etc.: bis(4-hydroxyphenyl)ketone: and halogen-substituted products of these bisphenols, such as 2,2-bis(4-hydroxy-
3,5-dichlorophenyl)propane, 2,2-
Bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-
3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3-bromo-5-chlorophenyl)propane, 2,2-bis(4- hydroxy-3,5-dichlorophenyl)
Butane, 2,2-bis(4-hydroxy-3,5
-dibromophenyl)butane, bis(4-hydroxyphenyl)-bis(difluoromonochloromethyl)methane, 1,3-dichloro-1′,1″,3′,
3″-tetrafluoro-2,2-bis(4-hydroxy-3,5-dichlorodiphenyl)propane,
1,3-dichloro-1',1'',3',3''-tetrafluoro-2,2-bis(4-hydroxy-3,5-
Examples include dibromodiphenyl)propane. These dihydric phenols may be homopolymers of dihydric phenols, copolymers of two or more types, or brind products. The polycarbonate resin used in the present invention preferably has a viscosity average molecular weight of 10,000 to 100,000, particularly 20,000 to 100,000, from the viewpoint of mechanical strength and moldability.
~40000 is preferred. In addition to polycarbonate resin, the flame-retardant resin composition of the present invention may also include polyolefin resins (polypropylene, polyethylene, ethylene-propylene copolymer, etc.), polystyrene, styrene-maleic anhydride, etc., as long as the properties are not impaired. Acid copolymer (SMA resin), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester (polyethylene terephthalate, etc.),
Polyamide (6-nylon, 6,6-nylon,
(6,12-nylon, etc.), acrylic resin, polyvinyl chloride resin, etc. can be blended. especially
SMA resin, AS resin, ABS resin, etc. are suitably blended. The polytetrafluoroethylene of the present invention is prepared by subjecting tetrafluoroethylene to a free radical catalyst in an aqueous solvent.
In the presence of e.g. sodium, potassium or ammonium peroxydisulfide, 100 to
Under 100psi pressure, 0-200℃, preferably 20-100
It can be obtained by polymerization at a temperature of °C. The amount of polytetrafluoroethylene used in the flame retardant resin composition of the present invention is 100% of the thermoplastic resin.
0.01 to 2 parts by weight, preferably 0.05 to 2 parts by weight
1 part by weight. If the amount of polytetrafluoroethylene is less than 0.01, the flame retardant effect is small, and it is not effective to reduce the amount of flame retardant and flame retardant aid while maintaining flame retardancy, and prevent a significant decrease in mechanical strength. do not have. On the other hand, if it exceeds 2 parts by weight, it causes poor appearance of the molded product. The flame retardant consisting of an organic halogen compound used in the present invention is not particularly limited as long as it is commonly used, but specific examples include hexabromobenzene, pentabromotoluene, biphenyl bromide, triphenyl chloride, Diphenyl ether, tetrachlorophthalic acid, tetrabromophthalic anhydride, tribromophenol, tribromophenyl, dibromoalkyl diphenyl ether, tetrabromobisphenol S, tetrachlorobisphenol A, 2,2-bis(4-hydroxy) −
In addition to 3,5-dibromophenyl)-propane, tetrabromobisphenol sulfone, and tetrabromobisphenol ether, aromatic halogen compounds represented by the following formulas can be mentioned. Further specific examples of organic halogen compounds that can be used as flame retardants in the present invention include alicyclic halogen compounds such as monochloropentabromocyclohexane, hexabromocyclododecane, perchloropentacyclodecane, and hexachloroendomethylenetetrahydrophthalic anhydride. , as well as chlorinated paraffin, chlorinated polyethylene, tetrabromoethane, tetrabromobutane, tris (β-chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (dibromopropyl)
Phosphate, Tris (chlorobromopropyl)
Aliphatic halogen compounds such as phosphates can be mentioned. These flame retardants may be used alone or in combination of two or more. The amount of the flame retardant in the flame retardant resin composition of the present invention is 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the thermoplastic resin. If the amount of the flame retardant is less than 0.1 parts by weight, insufficient flame retardance will be obtained, while if it exceeds 30 parts by weight, mechanical strength will decrease and discoloration will occur due to bleeding of the flame retardant. The flame retardant aid used in the flame retardant resin composition of the present invention is not particularly limited as long as it promotes the flame retardant effect of the above flame retardant, and examples thereof include antimony compounds, borates, etc. . As the antimony compound, antimony trioxide, sodium antimonate, antimony metal, antimony trichloride, antimony pentachloride, antimony trisulfide, antimony pentoxide, etc. can be used. In addition, borates include zinc borates such as zinc tetraborate, zinc metaborate, and basic zinc borate; barium borates such as barium orthoborate, barium metaborate, barium diborate, and barium tetraborate; lead borate,
Cadmium borate, magnesium borate, etc. can be used. These flame retardant aids may be used alone or in combination of two or more. The amount of flame retardant aid in the flame retardant resin composition of the present invention is
0.1 to 15 parts by weight per 100 parts by weight of thermoplastic resin,
Preferably it is 0.5 to 10 parts by weight. If the amount of the flame retardant auxiliary agent is less than 0.1 part by weight, the effect of promoting flame retardancy will be insufficient, while if it exceeds 15 parts by weight, the mechanical strength will decrease. The flame-retardant resin composition of the present invention may contain inorganic fillers, colorants, various additives, elastomers, etc., as necessary, within a range that does not impair the purpose of the present invention. The inorganic filler is blended for the purpose of improving or increasing the mechanical strength and durability of the flame-retardant resin composition, and includes, for example, glass fibers, glass beads, glass balloons,
Glass flakes, glass powder, calcium carbonate, calcium sulfate, talc, clay, mica,
Magnesium carbonate, dolomite, silica, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, pumice powder, magnesium sulfate, barium sulfate, calcium sulfite, asbestos, calcium silicate, montmorillonite, bentonite, carbon black, graphite , iron powder, lead powder, aluminum powder, molybdenum sulfide, and the like can be used alone or in combination of two or more. The pigment of the coloring agent is phthalocyanine,
Organic pigments such as quinacridone and benzidine,
Mention may be made of oxides, sulfides, and sulfates of metals such as titanium, lead, zinc, and cadmium, and inorganic pigments such as carbon black and aniline black produced by the furnace or impact method. Examples of the dye include azo, anthraquinone, thioindigo, quinoline, and indanthrene dyes. In addition, the various additives include, for example, hindered phenol type, phosphorus type such as phosphite type and phosphate type, antioxidants such as amine type, and ultraviolet absorbers such as benzotriazole type and benzophenone type. , external lubricants such as aliphatic carboxylic acid esters and paraffins, mold release agents, antistatic agents, and plasticizers. Examples of the elastomer include IIR, SBR, EPR, and acrylic elastomer. The flame retardant resin composition of the present invention comprises a polycarbonate resin, a flame retardant and a flame retardant aid consisting of polytetrafluoroethylene and an organic halogen compound as essential components, and each of the above additive components as desired. It can be prepared by blending and melt-kneading in the following proportions. This blending and kneading is
Commonly used methods such as ribbon blender, Henschel mixer, Banbury mixer,
This can be carried out by a method using a drum tumbler, single-screw extruder, twin-screw extruder, co-kneader, multi-screw extruder, or the like.
The appropriate heating temperature during kneading is usually in the range of 250 to 300°C. The flame-retardant resin composition thus obtained can be molded using various molding methods, such as injection molding, extrusion molding, compression molding, calendar molding, and rotary molding, to produce housings and parts for home appliances, OA equipment, etc. It is possible to manufacture molded products such as [Example] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. Examples As resins to be blended with polycarbonate resin (PC resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), styrene-maleic anhydride copolymer (SMA resin) , brominated polyphenylene oxide (brominated PPO) and di-tribromophenoxyethane were prepared as a flame retardant made of an organic halogen compound, and antimony trioxide was prepared as a flame retardant aid. Each component was mixed in the proportions shown in Table 1, melted and kneaded, and then injection molded to prepare a test piece. The obtained test pieces were evaluated for flame retardancy, Izod impact strength,
Tensile elongation was measured. The results are shown in Table 1.

〔Effect of the invention〕

According to the present invention, since the amount of flame retardant and flame retardant aid can be significantly reduced, it is possible to obtain a flame retardant resin composition that has excellent flame retardancy and mechanical strength. , its industrial value is great.

Claims (1)

[Claims] 1 For 100 parts by weight of polycarbonate resin,
1. A flame-retardant resin composition comprising 0.01-2 parts by weight of polytetrafluoroethylene, 0.1-30 parts by weight of a flame retardant made of an organic halogen compound, and 0.1-15 parts by weight of a flame retardant aid.