JP4936309B2 - Flame retardant polycarbonate resin composition with excellent moldability. - Google Patents

Description

  The present invention relates to a polycarbonate resin composition excellent in molding processability. More specifically, the polycarbonate resin has a specific and significant improvement in fluidity, flame retardancy, and rigidity without deteriorating the heat resistance, thermal stability, etc., which are characteristic of the polycarbonate resin. Relates to the composition.

  Polycarbonate resin is a thermoplastic resin excellent in impact resistance, transparency, heat resistance, thermal stability, and the like, and is widely used in fields such as electricity, electronics, ITE, machinery, and automobiles. On the other hand, in addition to these excellent performances of the resin, in each of the above-mentioned fields, a material having high flame retardancy and fluidity (formability) is required in order to satisfy safety and design requirements. It has been demanded.

  Conventionally, flame retardants such as organic bromine compounds and phosphorus compounds have been used, but recently, flame retardant materials that do not use these flame retardants have been demanded in consideration of environmental impact.

On the other hand, in order to improve the fluidity of the polycarbonate resin, as shown below, various techniques have been proposed from the past, but all have advantages and disadvantages, and further improvement methods have been demanded.
JP 2001-226576 A JP 2000-319497 A JP 2000-103951 A

Further, as a light reflecting plate material for liquid crystal display devices and the like, conventionally, a large amount of titanium oxide has been blended in a polycarbonate resin in order to obtain the desired light reflectivity. Attempts have also been made to obtain desired light reflectivity by treating titanium oxide.
JP 2005-320457 A JP 2005-015655 A JP 2003-183491 A

  As described above, as a general method for improving the fluidity of a polycarbonate resin, it has been proposed that a low molecular weight plasticizer or a polymer having a high fluidity is blended. There is a fundamental problem that the performance is greatly impaired, and there has been a strong demand for improvement. In addition, when a low molecular weight plasticizer is blended, the flame retardancy is lowered, and it is difficult to use in the electric, electronic, and ITE fields, which require particularly high flame retardancy, and the improvement has been desired. .

  In addition, the light-reflective flame-retardant polycarbonate resin contains a large amount of titanium oxide, so the thermal stability and molding processability during injection molding are poor, and the surface appearance and impact resistance of the molded product are reduced. However, these improvements have been desired.

  As a result of studies to solve the above problems, the present inventors have blended a polycarbonate resin with a specific structure silicon compound, organometallic salt compound, fiber-forming fluorine-containing polymer, organic acid and amide compound. It has been found that a flame retardant polycarbonate resin composition having excellent thermal stability and molding processability during injection molding, and excellent surface appearance and impact resistance of the molded product can be obtained. Has found that a flame retardant polycarbonate resin composition having light reflectivity can be obtained by adding and compounding a titanium compound, and has completed the present invention.

That is, according to the first aspect of the present invention, per 100 parts by weight of the polycarbonate resin (A), the main chain has a branched structure and the organic functional group contained is composed of an aromatic group, or an aromatic group and a hydrocarbon group (aromatic group). 0.01 to 1 part by weight of a silicone compound (B) excluding a group), 0.005 to 2 parts by weight of an organometallic salt compound (C), 0.01 to 2 parts of a fiber-forming fluorine-containing polymer (D) 5 parts by weight, 0.01 to 0.6 parts by weight of organic acid (E) and 0.4 to 1.0 parts by weight of amide compound (F) A resin composition is provided.

In addition, the second aspect of the present invention is that, per 100 parts by weight of the polycarbonate resin (A), the main chain has a branched structure and the organic functional group contained contains an aromatic group, or an aromatic group and a hydrocarbon group ( 0.01 to 1 part by weight of a silicone compound (excluding aromatic groups), 0.005 to 2 parts by weight of an organic metal salt compound (C), 0.01 of a fiber-forming fluorine-containing polymer (D) -5 parts by weight, organic acid (E) 0.01-0.6 parts by weight, amide compound (F) 0.4-1.0 parts by weight and titanium oxide (G) 5-25 parts by weight A light-reflective flame-retardant polycarbonate resin composition excellent in molding processability and a light-reflecting plate comprising the same are provided.

The flame-retardant polycarbonate resin composition excellent in moldability, which is the first aspect of the present invention, is excellent in thermal stability and moldability during injection molding, and has good surface appearance and impact resistance of the molded product. Therefore, it can be suitably used as a housing or part of a product in electricity, electronics, ITE, etc., and has an extremely high industrial utility value.
Further, the light-reflective flame-retardant polycarbonate resin composition excellent in molding processability according to the second aspect of the present invention is excellent in thermal stability and molding processability at the time of injection molding. The impact resistance is good, and it can be suitably used as a light reflecting plate material for liquid crystal display devices, lighting fixtures, LED display panels and the like.

  The polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted or a transesterification method obtained by reacting a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate. A typical example is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like.

  These are used singly or as a mixture of two or more types, but are preferably not substituted with halogen from the viewpoint of preventing discharge of the gas containing the halogen into the environment during combustion. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be mixed and used.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  The viscosity average molecular weight of the polycarbonate resin (A) is usually 10,000 to 100,000, preferably 15,000 to 35,000. In producing such a polycarbonate resin, a molecular weight regulator, a catalyst and the like can be used as necessary.

Silicone compound (B) in which the main chain used in the present invention has a branched structure and the organic functional group contained is composed of an aromatic group or composed of an aromatic group and a hydrocarbon group (excluding an aromatic group) Is represented by the following general formula (1).
General formula (1)

  In the general formula (1), R1, R2 and R3 represent main chain organic functional groups, and X represents a terminal functional group.

The silicone compound (B) is characterized by having T units (RSiO _1.5 ) and / or Q units (SiO _2.0 ) as branching units. These preferably contains more than 20 mol% of the total siloxane units _{(R 3~0 SiO 2~0.5).} (R represents an organic functional group.) In addition, the silicone compound (B) preferably contains 20 mol% or more of aromatic groups among the organic functional groups contained.

  The aromatic group contained is phenyl, biphenyl, naphthalene or a derivative thereof, but a phenyl group can be preferably used.

  Of the organic functional groups in the silicone compound (B) attached to the main chain or branched side chain, the organic group other than the aromatic group is preferably a hydrocarbon group having 4 or less carbon atoms, and preferably a methyl group. Can be used. Further, the terminal group is preferably one kind selected from methyl group, phenyl group and hydroxyl group, or a mixture of these two kinds to three kinds.

  The average molecular weight (weight average) of the silicone compound (B) is preferably 3000 to 500000, and more preferably 5000 to 270000.

The amount of the silicone compound (B) is a polycarbonate resin (A) 0.01 to 1 part by weight per 100 parts by weight. If the blending amount is outside the range, the flame retardant effect is insufficient in any case, which is not preferable. More preferably, it is 0.05 to 1 part by weight.

  Examples of the organic metal salt compound (C) used in the present invention include aromatic sulfonic acid metal salts and perfluoroalkanesulfonic acid metal salts, and preferably 4-methyl-N- (4-methyl). Phenyl) sulfonyl-benzenesulfonamide potassium salt, potassium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-3'-disulfonate, sodium paratoluenesulfonate, potassium perfluorobutanesulfonate, and the like can be used.

  The compounding amount of the organometallic salt compound (C) is 0.005 to 2 parts by weight per 100 parts by weight of the polycarbonate resin (A). If the blending amount is less than 0.005 parts by weight, the flame retardancy is lowered, which is not preferable. Moreover, when a compounding quantity exceeds 2 weight part, since a mechanical property and a flame retardance fall or surface appearance deteriorates, it is unpreferable. More preferably, it is 0.1 to 1 part by weight.

The fiber-forming fluorine-containing polymer (D) used in the present invention is preferably one that forms a fibril-like structure in the polycarbonate resin (A). For example, polytetrafluoroethylene, a tetrafluoroethylene copolymer (For example, tetrafluoroethylene / hexafluoropropylene copolymer, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonates produced from fluorinated diphenols, and the like. In particular, polytetrafluoroethylene having a molecular weight of 1,000,000 or more and a fibril-forming ability having a secondary particle diameter of 100 μm or more is preferably used.
As a commercially available raw material, Daikin Industries, Ltd., neoflon FA500, etc. are mentioned.

  The amount of the fiber-forming fluoropolymer (D) is 0.01 to 5 parts by weight per 100 parts by weight of the polycarbonate resin (A). If the blending amount is less than 0.01 parts by weight, the effect of preventing dripping is inferior and the flame retardancy is lowered, which is not preferable. On the other hand, if the blending amount exceeds 5 parts by weight, the surface appearance and impact resistance deteriorate, which is not preferable. More preferably, it is 0.1-1 weight part, More preferably, it is 0.2-0.5 weight part.

  As the organic acid (E) used in the present invention, various types can be used. Examples thereof include fatty acids having 6 to 30 carbon atoms, and typical examples include caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, arachidic acid, maleic anhydride, and acid-modified siloxane. In particular, capric acid is preferably used.

  The compounding quantity of organic acid (E) is 0.01-0.6 weight part per 100 weight part of polycarbonate resin (A). If the blending amount is less than 0.01 parts by weight, the fluidity is inferior. If the blending amount exceeds 0.6 parts by weight, the impact strength is lowered, or appearance defects such as silver are generated at the time of molding, which is not preferable. More preferably, it is 0.05 to 0.2 parts by weight.

The amide compound (F) used in the present invention is a compound represented by the following general formula (2).
General formula (2)
_{R1-CONH- (CH 2) n} -NHCO-R2
However, R1 and R2 are linear or branched alkyl groups having 6 to 30 carbon atoms, and n is an integer of 2 to 6. Specific examples include ethylene bisstearyl amide and ethylene bis oleyl amide, and ethylene bisstearyl amide is particularly preferable.

  The compounding quantity of an amide compound (F) is 0.4-1.0 weight part per 100 weight part of polycarbonate resin (A). If the blending amount is less than 0.4 parts by weight, the fluidity is inferior, and if it exceeds 1.0 parts by weight, the impact strength is lowered or appearance defects such as silver occur at the time of molding. More preferably, it is 0.5 to 0.8 part by weight.

  The titanium oxide (G) used in the present invention may be produced by either the chlorine method or the sulfuric acid method, and the crystal form thereof may be either a rutile type or an anatase type. In addition, titanium oxide having a particle size of about 0.1 to 0.5 μm can be suitably used.

  The compounding quantity of a titanium oxide (G) is 5-25 weight part per 100 weight part of polycarbonate resin (A). If the blending amount is less than 5 parts by weight, the light reflectivity is poor. More preferably, it is 9 to 16 parts by weight.

  In addition, various heat stabilizers, antioxidants, colorants, fluorescent brighteners, mold release agents, softeners, antistatic agents and other additives, inorganic fillers, impacts, etc., as long as the effects of the present invention are not impaired. You may mix | blend property improvement material and other resin.

  There are no particular limitations on the method of mixing the various blending components in the polycarbonate resin composition of the present invention, and examples thereof include mixing with a known mixer such as a tumbler or ribbon blender or melt kneading with an extruder.

  Moreover, there is no restriction | limiting in particular also in the method of shape | molding the polycarbonate resin composition of this invention, A well-known injection molding method, injection / compression molding method, etc. can be used.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. “Parts” are based on weight unless otherwise specified.

The following were used as raw materials.
(A) Polycarbonate resin:
Caliber 200-20 manufactured by Sumitomo Dow
(B) Silicone compound:
The silicone compound was produced according to a general production method. That is, a silicone compound partially condensed by dissolving an appropriate amount of diorganodichlorosilane, monoorganotrichlorosilane and tetrachlorosilane, or a partially hydrolyzed condensate thereof in an organic solvent, adding water and hydrolyzing it. Then, triorganochlorosilane was added and reacted to terminate the polymerization, and then the solvent was separated by distillation or the like. The structural characteristics of the silicone compound synthesized by the above method are as follows:
・ D / T / Q unit ratio of main chain structure: 40/60/0 (molar ratio)
-Ratio of phenyl group in all organic functional groups (*): 60 mol%
-Terminal group: methyl group only-Weight average molecular weight (**): 15000
*: The phenyl group is first contained in the T unit in the silicone containing the T unit, and the remaining D group is contained in the D unit. When the phenyl group is attached to the D unit, the one attached is preferential, and when the phenyl group remains, two are attached. Except for the terminal group, the organic functional group is a methyl group except for the phenyl group.
**: Weight average molecular weight is two significant digits.

(C) Organometallic salt:
Sodium paratoluenesulfonate (D) fiber-forming fluorine-containing polymer (hereinafter abbreviated as “PTFE”):
NEOFRON FA500 manufactured by Daikin Industries
(E) Organic acid:
Capric acid NAA-102 manufactured by NOF Corporation
(F) Amide compound:
Ethylene bisstearylamide Alflow H-50TF made by Nippon Oil & Fats
(G) Titanium oxide:
Titanium dioxide: 2230 manufactured by Kronos

  The above-mentioned various raw materials are collectively put into a tumbler at the blending ratios shown in Tables 2 to 4, and after dry mixing for 10 minutes, using a twin-screw extruder (KTX37 manufactured by Kobe Steel) to a melting temperature of 280 ° C. And kneaded to obtain various pellets of the polycarbonate resin composition.

  Various test pieces were prepared from the obtained pellets using an injection molding machine (J100E-C5 manufactured by Nippon Steel Works), and various data were collected by the following methods.

(1) Archimedes spiral flow fluidity:
The flow length at a channel thickness of 1 mm was measured using an Archimedes spiral flow mold under a melting temperature of 280 ° C. A flow length of 130 mm or more was regarded as acceptable.

(2) Flame resistance:
The flammability was evaluated according to the following UL94V vertical combustion test method. The test piece is left for 48 hours in a temperature-controlled room with a temperature of 23 ° C. and a humidity of 50%. Was evaluated. UL94V is a method for evaluating flame retardance from the afterflame time and drip properties after indirect flames of a burner for 10 seconds on a test piece of a predetermined size held vertically, and is divided into the following classes: . Samples that do not fit the following classes are scored as non-conforming (NR).

(3) Light reflectivity: A three-stage plate (thickness 3, 2, 1 mm) test piece having a length of 90 mm and a width of 40 mm was prepared, and a Y value at a wavelength of 400 to 800 nm was measured for a portion of 1 mm thickness by a spectrophotometer (Murakami). Color Technology Laboratory CMS-35SP). A sample having a Y value of 94% or more was regarded as acceptable.

  The after-flame time shown in Table 1 is the length of time that the specimen keeps flaming combustion after the ignition source is moved away. The ignition of cotton by drip is about 300 mm below the lower end of the specimen. It is determined by whether a certain marking cotton is ignited by a drip from the specimen. The evaluation standard was V-0 or higher in the 1.6 mm thickness test.

  As shown in Table 2, when the configuration of the present invention was satisfied (Examples 1 to 6), all the evaluation items had sufficient performance.

On the other hand, as shown in Table 3, when the configuration of the present invention was not satisfied, each case had some drawbacks.
Since Comparative Example 1 is a case where the blending amount of the organic acid is less than the standard, the fluidity was insufficient.
Since the comparative example 2 is a case where the compounding amount of the organic acid exceeds the regulation, the flame retardancy was insufficient.
Since the comparative example 3 is a case where the compounding quantity of an amide compound is less than prescription | regulation, fluidity | liquidity was inadequate.
Since the comparative example 4 is a case where the compounding quantity of an amide compound exceeds a prescription | regulation, flame retardance was inadequate.
Since the comparative example 5 is a case where the compounding quantity of a silicone compound is less than prescription | regulation, the flame retardance was inadequate.
Since the comparative example 6 is a case where the compounding quantity of the silicone compound exceeds the regulation, the flame retardancy was insufficient.
Since the comparative example 7 is a case where the compounding quantity of an organometallic salt compound is less than prescription | regulation, the flame retardance was inadequate.
Since the comparative example 8 is a case where the compounding quantity of PTFE is less than regulation, the flame retardancy was insufficient.

  As shown in Table 4, when the configuration of the present invention was satisfied (Examples 7 to 9), all the evaluation items had sufficient performance.

On the other hand, as shown in Comparative Example 9 in Table 4, when the blending amount of titanium oxide exceeded the specified range, the flame retardancy was insufficient.

Claims (7)

Silicone compound in which the main chain has a branched structure and the organic functional group contained is composed of an aromatic group or composed of an aromatic group and a hydrocarbon group (excluding the aromatic group) per 100 parts by weight of the polycarbonate resin (A). (B) 0.01 to 1 part by weight, organometallic salt compound (C) 0.005 to 2 parts by weight, fiber-forming fluoropolymer (D) 0.01 to 5 parts by weight, organic acid (E) 0 A flame-retardant polycarbonate resin composition excellent in molding processability, characterized by comprising 0.01 to 0.6 parts by weight and amide compound (F) 0.4 to 1.0 parts by weight. Silicone compound in which the main chain has a branched structure and the organic functional group contained is composed of an aromatic group or composed of an aromatic group and a hydrocarbon group (excluding the aromatic group) per 100 parts by weight of the polycarbonate resin (A). (B) 0.01 to 1 part by weight, organometallic salt compound (C) 0.005 to 2 parts by weight, fiber-forming fluoropolymer (D) 0.01 to 5 parts by weight, organic acid (E) 0 .01-0.6 parts by weight, amide compound (F) 0.4-1.0 parts by weight and titanium oxide (G) 5-25 parts by weight Flame retardant polycarbonate resin composition.   The flame retardant polycarbonate excellent in moldability according to claim 1 or 2, wherein the organic metal salt compound (C) is a metal salt of an aromatic sulfonic acid or a metal salt of a perfluoroalkanesulfonic acid. Resin composition.   The flame retardant polycarbonate resin composition excellent in molding processability according to claim 1 or 2, wherein the organic acid (E) is a fatty acid having 6 to 30 carbon atoms. The flame retardant polycarbonate resin composition excellent in molding processability according to claim 1 or 2, wherein the amide compound (F) is a compound represented by the following general formula.
Formula _{R1-CONH- (CH 2) n} -NHCO-R2
However, R1 and R2 are a C6-C30 linear or branched alkyl group, and n is an integer of 2-6.   A light reflecting plate obtained by molding the polycarbonate resin composition according to claim 2.   The light reflecting plate according to claim 6, which is used for a liquid crystal frame or a lamp holder.