JP6346077B2 - Antistatic polycarbonate resin composition having light diffusibility - Google Patents

Description

  The present invention relates to an antistatic polycarbonate resin composition having excellent thermal stability and light diffusibility. More specifically, the present invention relates to an antistatic polycarbonate resin composition that suppresses gas generation during molding by an antistatic agent and is excellent in light diffusibility.

  Polycarbonate resins are excellent in impact resistance, heat resistance, and transparency, and are widely used in fields such as electrical / electronic, optical, building materials, medical, food, and vehicles. However, products obtained from polycarbonate resin are easily charged with static electricity, and there are problems associated with static electricity, such as adhesion of dust to packaging materials and molded products, electric shock during molding and use, and malfunction of OA machines. Conventionally, various formulations of antistatic agents have been studied. Further, in lighting applications such as LED lighting covers and base light covers, high light diffusivity is required simultaneously with antistatic performance.

In order to impart antistatic performance to the polycarbonate resin, a phosphonium salt is blended as an antistatic agent. However, this composition does not sufficiently satisfy antistatic properties and thermal stability, and does not have light diffusibility.
In addition, a diglycerin fatty acid ester and an antioxidant are blended in a polycarbonate resin. (Patent Document 2) Although the antistatic performance is improved to some extent, this composition has a problem that a diglycerin fatty acid ester is decomposed and gas is generated during molding, and it does not have light diffusibility.

JP 2005-272678 A JP-A-2-196852

  The present invention improves the thermal stability by using an ester compound consisting of a specific polyhydric alcohol and a fatty acid as an antistatic agent, prevents the generation of a large amount of gas, and has an antistatic property having excellent light diffusibility. An object is to provide a polycarbonate resin composition.

  As a result of earnest research on the above-mentioned problems, the present inventor has found that a polycarbonate resin is blended with an ester compound composed of a specific polyhydric alcohol and a fatty acid, an epoxy polymer containing a glycidyl group, and a light diffusing agent. The inventors have found that an antistatic polycarbonate resin composition having improved stability, remarkably preventing the generation of a large amount of gas and excellent in light diffusibility can be obtained, and the present invention has been completed.

  That is, the present invention relates to (A) 100 parts by weight of a polycarbonate resin (component A), (B) 0.5 to 5 parts by weight of an ester compound (component B) composed of a polyhydric alcohol and a fatty acid, and (C) a glycidyl group. An epoxy polymer (component C) containing 0.003 to 0.5 parts by weight and (D) a light diffusing agent (component D) 0.05 to 15 parts by weight, and a hydroxy group of a polyhydric alcohol in the component B An antistatic polycarbonate resin composition having light diffusibility, and a molded article comprising the same, wherein the molar ratio (hydroxy group / carboxyl group) of the fatty acid to the carboxyl group of the fatty acid is in the range of 4-8.

  The antistatic polycarbonate resin composition having light diffusibility of the present invention is excellent not only in antistatic properties but also in thermal stability and light diffusibility, requires high light diffusibility, and avoids adhesion of dust. For example, it is suitably used for LED lighting glove covers and base light covers.

It is the schematic which shows the measuring method of the diffusivity in this invention.

Hereinafter, the present invention will be described in detail.
<About component A>
The polycarbonate resin used as the component A of the present invention is a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method obtained by a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted. A typical example is an aromatic 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 ' -Dihydroxydiaryl sulfoxides such as dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, dihydroxydiaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, etc. And the like.
These are used individually or in mixture of 2 or more types. 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 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.

<About B component>
The molar ratio (hydroxy group / carboxyl group) of the hydroxy group of the polyhydric alcohol and the carboxyl group of the fatty acid is 4 to 8 in the ester compound composed of the polyhydric alcohol and the fatty acid used as the B component of the present invention. The range is preferably 4-6, more preferably 4-5. When the molar ratio is less than 4, the antistatic property is inferior. When it exceeds 8, the thermal stability is deteriorated and a large amount of gas is generated.

  As polyhydric alcohol components, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, pentaerythritol, inositol, ribulose, xylulose, ribose, arabinose, xylose, lyxose, psicose, fructose, sorbose, tagatose, allose, Examples thereof include altrose, glucose, mannose, gulose, idose, galactose, talose, fucose, fucose, rhamnose, sedheptulose, sucrose, lactose, maltose, trehalose, tyranose, and cellobiose, among which diglycerin is preferably used.

  As the fatty acid, a fatty acid having 10 to 18 carbon atoms is preferably used. If the carbon number is less than 10, the sustainability of the antistatic performance may be inferior, and if the carbon number exceeds 18, the antistatic property may be inferior. Examples of the fatty acid having 10 to 18 carbon atoms include capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, and stearic acid.

  Specific examples of the ester compound comprising a polyhydric alcohol and a fatty acid include diglycerol monolaurate, diglycerol monomyristate, diglycerol monostearate, triglycerol monolaurate, triglycerol monomystate, triglycerol monostearate. Rate, tetraglycerol monolaurate, tetraglycerol monomyristate, tetraglycerol monostearate, pentaglycerol monolaurate, pentaglycerol monomyristate, pentaglycerol monostearate, hexaglycerol monolaurate, hexaglycerol monomyristate, Hexaglycerin monostearate, sucrose laurate, sucrose myristic ester, sucrose palmitate, sucrose stearate, etc. Is, preferably diglycerol monolaurate is used.

  Content of B component is 0.5-5 weight part with respect to 100 weight part of A component. Preferably it is 0.7-3 weight part, More preferably, it is 1-2 weight part. When the content is less than 0.5 parts by weight, the antistatic property is inferior. When the content exceeds 5 parts by weight, the thermal stability and light diffusibility are lowered, and a large amount of gas is generated.

<About component C>
The epoxy polymer containing a glycidyl group used as the component C of the present invention is preferably an epoxy polymer containing glycidyl methacrylate in the copolymer, and polystyrene is suitably used as the other component of the copolymer. It is done. When an epoxy polymer that does not contain a glycidyl group is used, the compatibility with the component A is poor, so that thermal stability and light diffusibility are lowered, and a large amount of gas is generated.

  As the monomer component of the polymer containing a glycidyl group, allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, Examples thereof include epoxy succinic acid, and examples of the polymer include terminal epoxy-modified polydimethylsiloxane and side chain epoxy-modified polydimethylsiloxane. Among these, a polyglycidyl methacrylate-polystyrene copolymer is preferably used.

  Content of C component is 0.003-0.5 weight part with respect to 100 weight part of A component, Preferably it is 0.01-0.1 weight part, More preferably, it is 0.03-0.05 weight. Part. If the content is less than 0.003 parts by weight, the thermal stability is inferior and decomposition gas is generated. If it exceeds 0.5 parts by weight, decomposition gas is generated from the epoxy polymer itself, which is not preferable.

<About D component>
The light diffusing agent used as the component D of the present invention may be any of organic fine particles typified by polymer fine particles and inorganic fine particles. The polymer fine particles are typically exemplified by organic crosslinked particles obtained by polymerizing a non-crosslinkable monomer and a crosslinkable monomer. Furthermore, other copolymerizable monomers other than such monomers can also be used. Examples of other organic crosslinked particles include silicone crosslinked particles typified by polyorganosilsesquioxane. Among these, polymer fine particles are preferable, and particularly organic crosslinked particles can be suitably used. In such organic crosslinked particles, examples of monomers used as non-crosslinkable monomers include non-crosslinkable vinyl monomers such as acrylic monomers, styrene monomers, and acrylonitrile monomers, and olefin monomers. Acrylic monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and phenyl methacrylate alone or in combination. Can be used. Of these, methyl methacrylate is particularly preferable. As the styrenic monomer, styrene, α-methyl styrene, methyl styrene (vinyl toluene), alkyl styrene such as ethyl styrene, and halogenated styrene such as brominated styrene can be used, and styrene is particularly preferable. . As the acrylonitrile monomer, acrylonitrile and methacrylonitrile can be used. As the olefin monomer, ethylene, various norbornene-type compounds, and the like can be used. Furthermore, glycidyl methacrylate, N-methylmaleimide, maleic anhydride, etc. can be illustrated as another copolymerizable monomer. As a result, the organic crosslinked particles of the present invention may have units such as N-methylglutarimide. On the other hand, examples of the crosslinkable monomer for the non-crosslinkable vinyl monomer include divinylbenzene, allyl methacrylate, triallyl cyanurate, triallyl isocyanate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and propylene glycol. (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane (meth) acrylate, pentaerythritol tetra (meth) acrylate, bisphenol A di (meth) acrylate, dicyclopentanyl di (meth) acrylate , Dicyclopentenyl di (meth) acrylate, N-methylol (meth) acrylamide, and the like.

  The average particle diameter of the light diffusing agent used as the D component of the present invention is preferably 1 to 30 μm, more preferably 1 to 10 μm, and further preferably 1 to 5 μm. If the average particle size is less than 1 μm or more than 30 μm, light diffusibility may be insufficient. The average particle diameter may be obtained by any of the laser diffraction / scattering method, coal tar method, and centrifugal sedimentation method, and is represented by a 50% value (D50) of the integrated particle size distribution. The particle size distribution may be single or plural. That is, it is possible to combine two or more light diffusing agents having different average particle diameters. However, a more preferred light diffusing agent has a narrow particle size distribution. It is more preferable to have a distribution containing 70% by weight or more of the particles in the range of 2 μm before and after the average particle diameter. The shape of the light diffusing agent is preferably close to a sphere from the viewpoint of light diffusibility, and more preferably a shape close to a true sphere. Such a sphere includes an elliptical sphere. The refractive index of the light diffusing agent used as the D component of the present invention is usually preferably in the range of 1.30 to 1.80, more preferably 1.33 to 1.70, still more preferably 1.35 to 1.80. A range of 65. These exhibit a sufficient light diffusion function in a state where they are blended in the resin composition. Content of D component is 0.05-15 weight part with respect to 100 weight part of A component, Preferably it is 0.1-10 weight part, More preferably, it is 0.1-3 weight part. If the D component is less than 0.05 parts by weight, the light diffusibility is insufficient, and if it exceeds 15 parts by weight, the light diffusibility is lowered and a large amount of gas is generated.

<About E component>
The resin composition of the present invention can contain a phosphorus-based antioxidant as the E component. Examples of the phosphorus-based antioxidant include at least one compound selected from the group consisting of phosphite-based antioxidants represented by the following general formulas (1) to (3).

  In General formula (1), R1-R4 shows a C1-C20 alkyl group or an aryl group. R1 to R4 may be the same or different. Preferable examples of R1 to R4 include 2,4-di-tert-butylphenyl.

  In General formula (2), R5 and R6 represent a C1-C20 alkyl group or an aryl group. R5 and R6 may be the same or different. Preferable examples of R5 and R6 include 2,4-di-tert-butylphenyl.

  In General formula (3), Ar shows the aryl group which may be substituted by a C1-C20 alkyl group. Ar may be the same or different. Preferable examples of the substituent represented by Ar include 2,4-di-tert-butylphenyl.

  The content of the E component is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and still more preferably 0.02 to 0. 1 part by weight. If the content is less than 0.005 parts by weight, the thermal stability may be inferior, and if it exceeds 1 part by weight, the hue may deteriorate, which is not preferable.

<About F component>
As the metal salt flame retardant used as the F component of the present invention, a fluorine-containing organic metal salt compound, particularly a perfluoroalkylsulfonic acid metal salt is preferably used. The metal constituting the metal ion of the perfluoroalkylsulfonic acid metal salt is preferably an alkali metal or an alkaline earth metal. Therefore, a more suitable metal salt flame retardant is an alkali (earth) metal salt of perfluoroalkyl sulfonate. (Here, the notation of alkali (earth) metal salt is used in the meaning including both alkali metal salt and alkaline earth metal salt). Examples of the alkali metal include lithium, sodium, potassium, rubidium and cesium, Alkaline earth metals include beryllium, magnesium, calcium, strontium and barium. More preferred is an alkali metal. Among such alkali metals, rubidium and cesium are suitable when transparency requirements are higher, but these are not general-purpose and difficult to purify, resulting in disadvantages in terms of cost. is there. On the other hand, although lithium and sodium are advantageous in terms of cost and flame retardancy, they may be disadvantageous in terms of transparency. Taking these into consideration, the alkali metal in the alkali metal perfluoroalkyl sulfonate can be properly used, but potassium perfluoroalkyl sulfonate having an excellent balance of properties is most suitable in any respect. Such potassium salts and alkali metal salts of perfluoroalkylsulfonic acid composed of other alkali metals can be used in combination.

  Such alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, perfluorobutanesulfone. Acid sodium, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, Cesium perfluorooctane sulfonate, cesium perfluorohexane sulfonate, perfluorobutene Nsuruhon acid rubidium, and perfluorohexane sulfonic acid rubidium, and the like. These can be used alone or in combination of two or more. Of these, potassium perfluorobutanesulfonate is particularly preferred. The content of the fluorine-containing organometallic salt compound is preferably 0.0001 to 1.0 part by weight, more preferably 0.001 to 0.5 part by weight, and further preferably 100 parts by weight of component A. 0.001 to 0.3 parts by weight, particularly preferably 0.005 to 0.2 parts by weight. The effect which is anticipated by the blending of the fluorine-containing organometallic salt compound is exhibited as the preferable range is reached. In addition, as an organic metal salt flame retardant other than the above-mentioned fluorine-containing organic metal salt compound, a metal salt of an organic sulfonic acid not containing a fluorine atom is suitable. Examples of the metal salt include an alkali metal salt of an aliphatic sulfonic acid, an alkaline earth metal salt of an aliphatic sulfonic acid, an alkali metal salt of an aromatic sulfonic acid, and an alkaline earth metal salt of an aromatic sulfonic acid (any Also does not contain a fluorine atom).

  Preferable examples of the aliphatic sulfonic acid metal salt include alkali (earth) metal salts of alkyl sulfonic acid, and these can be used alone or in combination of two or more. Preferred examples of the alkane sulfonic acid used for the alkali (earth) metal salt of the alkyl sulfonate include methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, methyl butane sulfonic acid, hexane sulfonic acid, and heptane. Examples thereof include sulfonic acid and octanesulfonic acid, and these can be used alone or in combination of two or more.

  The aromatic sulfonic acid used in the aromatic (earth) metal salt of aromatic sulfonate includes monomeric or polymeric aromatic sulfide sulfonic acid, aromatic carboxylic acid and ester sulfonic acid, monomeric or polymeric sulfonic acid. Aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonic acid, aromatic ketone sulfonic acid, heterocyclic sulfonic acid, Examples include at least one acid selected from the group consisting of sulfonic acids of aromatic sulfoxides and condensates of methylene type bonds of aromatic sulfonic acids, and these are used alone or in combination of two or more. be able to.

  Specific examples of the aromatic (earth) metal salt of an aromatic sulfonate include, for example, disodium diphenyl sulfide-4,4′-disulfonate, dipotassium diphenyl sulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate Poly (1,3-phenylene oxide) polysulfonic acid polysodium, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid poly Lithium, poly (2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2 , 6-disulfonic acid dipotassium, biphenyl-3,3'-disulfonic acid calcium, diphenylsulfone-3-sulfonic acid sodium, diphenylsulfone-3-sulfonic acid potassium, diphenylsulfone-3,3'-disulfonic acid dipotassium, diphenylsulfone -3,4'-dipotassium disulfonate, α, α, α-trifluoroacetophenone-4-sodium sulfonate, dipotassium benzophenone-3,3'-disulfonate, thiof 2,5-disulfonic acid disodium, thiophene-2,5-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid calcium, benzothiophene sodium sulfonate, diphenyl sulfoxide-4- potassium sulfonate, naphthalene sulfone Examples thereof include a formalin condensate of sodium acid and a formalin condensate of sodium anthracene sulfonate.

  On the other hand, the alkali (earth) metal salt of sulfate ester may include, in particular, the alkali (earth) metal salt of sulfate ester of monovalent and / or polyhydric alcohols. Alcohol sulfates include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono, di, tri, tetrasulfate, and lauric acid monoglyceride. And sulfuric acid esters of palmitic acid monoglyceride and stearic acid monoglyceride sulfate. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate.

Examples of other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N Examples include-(N'-benzylaminocarbonyl) sulfanilimide and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanilimide.
Among the above, preferable metal salts of organic sulfonic acids not containing fluorine atoms are aromatic (earth) metal salts of aromatic sulfonates, and potassium salts are particularly preferable.
The content of the aromatic (earth) metal salt of the aromatic sulfonate is preferably 0.0001 to 1.0 part by weight, more preferably 0.001 to 0.5 part by weight, more preferably 100 parts by weight of the component A Preferably it is 0.008-0.2 weight part.

<Other ingredients>
The antistatic polycarbonate resin composition having light diffusibility of the present invention can be used in combination with other antistatic agents as long as the effects of the present invention are not impaired. As other antistatic agents that can be used in combination, widely known ones can be used, and examples thereof include alkylsulfonates, alkylbenzenesulfonates, ammonium salts, and other phosphonium salts. It is not limited to. Furthermore, known additives such as glass fibers (chopped strands, milled fibers, etc.), heat stabilizers, mold release agents, ultraviolet absorbers, flame retardant aids, as long as the effects of the present invention are not impaired as required. Additives such as fluorescent brighteners and dyes / pigments may be added.

<Manufacture of resin composition>
The resin composition of the present invention comprises a tumbler, a V-type blender, a nauter mixer, a Banbury mixer, a kneading roll, and an extruder in which A component, B component, C component, D component and optionally other components are simultaneously or in any order. It can mix and manufacture with mixers, such as. Preferably, melt kneading with a twin-screw extruder is preferred, and if necessary, it is preferable to supply an optional component into the other melt-mixed component from the second supply port using a side feeder or the like.

<About molded products>
A molded product using the resin composition of the present invention can be obtained by molding the pellets produced as described above. Preferably, it is obtained by injection molding or extrusion molding. In injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, and heat insulation gold Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, multicolor molding, sandwich molding, and ultrahigh-speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding. In extrusion molding, various shaped extrusion molded products, sheets, films and the like are obtained. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can also be formed into a molded product by rotational molding, blow molding or the like.

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.
Based on the blending components and blending amounts shown in Table 1, various blending components were mixed using a tumbler and melt kneaded at a cylinder temperature of 270 ° C. using a twin screw extruder (TEX-30α manufactured by Nippon Steel) Pellets were obtained.

In addition, the compounding component used is as follows, respectively.
1. A component PC: Panlite L-1225WP manufactured by Teijin Ltd. (viscosity average molecular weight: 22400)

2. B component B-1: Diglycerin monolaurate (molar ratio of hydroxy group of polyhydric alcohol to carboxyl group of fatty acid (hydroxy group / carboxyl group) is 4) (Poem DL-100 manufactured by Riken Vitamin Co., Ltd.)
B-2: Sucrose fatty acid ester (molar ratio of hydroxy group of polyhydric alcohol and carboxyl group of fatty acid (hydroxy group / carboxyl group) is 8) (Daiichi Kogyo Co., Ltd. DK Ester SS)
B-3: Glycerol monostearate (molar ratio of hydroxy group of polyhydric alcohol to carboxyl group of fatty acid (hydroxy group / carboxyl group) is 3) (Riken Vitamin Rikemar S-100A)
B-4: Decaglycerin lauric acid ester (molar ratio of hydroxy group of polyhydric alcohol to carboxyl group of fatty acid (hydroxy group / carboxyl group) is about 10) (Mitsubishi Chemical Foods Corporation Ryoto Polyglyceride L-10D)

3. Component C-1: Polyglycidyl methacrylate-polystyrene block copolymer (Mafproof G0250SP manufactured by NOF Corporation)
C-2: Side chain epoxy-modified polydimethylsiloxane (KF-1001 manufactured by Shin-Etsu Chemical Co., Ltd.)
C-3: Alicyclic epoxy polymer (Epoxy compound EHPE3150 manufactured by Daicel Corporation)

4). D component D-1: bead-shaped crosslinked silicone (Momentive Performance Materials Japan GK Co., Ltd .: Tospearl 120 (trade name), average particle size 2 μm)
D-2: Beaded crosslinked silicone (Momentive Performance Materials Japan GK Co., Ltd .: Tospearl 145 (trade name), average particle size 5 μm)
D-3: Bead-like crosslinked acrylic particles (manufactured by Sekisui Plastics Co., Ltd .: MBX-5 (trade name), average particle diameter 5 μm)
D-4: Beaded crosslinked acrylic particles (manufactured by Sekisui Plastics Co., Ltd .: MBX-30 (trade name), average particle size 30 μm)
D-5: Calcium carbonate (Cypro Kasei Co., Ltd. product: Cypron A (trade name), average particle size 10 μm)

5. E component E-1: Phosphite-based antioxidant (P-EPQ manufactured by ADEKA)

6). F component F-1: perfluorobutanesulfonic acid potassium salt (Megafac F114P manufactured by DIC Corporation)

  Next, by using an injection molding machine (Toshiba Machine IS-150EN) using the obtained pellets, various test pieces were prepared at a cylinder setting temperature of 320 ° C and a mold temperature of 80 ° C. Carried out.

1. Antistatic property A flat plate of 90 mm × 50 mm × 2 mm was prepared by injection molding and measured under the following conditions. After the plate test piece was conditioned for 24 hours or more at 23 ° C. and 50% relative humidity, the surface resistivity was measured using a superinsulator (Digital Super Insulation DSM-8104 manufactured by Hioki Electric Co., Ltd.) at a measurement voltage of 100V. Was measured. A surface resistivity of 1 × 10 ¹⁴ Ω / □ or less was accepted.

2. Thermal stability When a 90 mm × 50 mm × 2 mm flat plate was formed by injection molding, it was retained for 10 minutes in a cylinder at a set temperature of 320 ° C. The hues of the molded product during stay molding and the molded product during normal molding were measured according to ASTM D-1925. The difference between the molded product at the stay molding and the molded product at the normal molding was ΔE, and 5 or less was accepted. ΔE is defined by the following equation.
ΔE = {(ΔL) ² + (Δa) ² + (Δb) ² } ^1/2
Hue of “flat plate obtained from normal molding”: L, a, b
Hue of “flat plate obtained from stay forming”: L ′, a ′, b ′
ΔL: LL ′
Δa: aa ′
Δb: bb ′

3. Gas generation When forming a 90mm x 50mm x 2mm flat plate by injection molding, visually confirm the generation of gas from the purge ball after purging for 10 minutes in a cylinder with a set temperature of 320 ° C. did. The case where the generated gas was not visible within 5 shots after the start of the purging operation was indicated as “◯”, and the case where the generated gas was not visible after exceeding 5 shots was indicated as “X”.

4). Light Diffusivity The diffusivity of a flat test piece having a side of 150 mm and a thickness of 2 mm was measured using a goniophotometer manufactured by Nippon Color Technology Laboratory Co., Ltd. The measurement method in that case is shown in FIG. Note that the diffusivity is the angle of γ when the amount of transmitted light is 50 when the amount of transmitted light is 100 when γ = 0 degrees when a light beam is vertically applied to the specimen surface in FIG. . When the flat plate surface is smooth, the relationship between the diffusivity and the addition amount of the diffusing agent is generally expressed by the following formula. However, when silver or burns are generated on the flat plate surface, the following formula does not apply. When the value of γ is in the range of ± 2 from the following theoretical value, “◯” is given, and the others are “x”.
Y = 60x (0 ≦ x ≦ 1)
Y = 60 (x> 1)
x: Amount of diffusing agent added (parts by weight)
Y: Angle of diffusivity γ The test results are shown in Tables 1 and 2.

As shown in Examples 1 to 15, the polycarbonate resin composition having the requirements of the present invention satisfies all the required performance including the surface specific resistance value.
On the other hand, in the case where the requirements of the present invention were not satisfied, each case had some drawbacks. In Comparative Example 1, the content of the antistatic agent was small, and the surface resistance did not satisfy the required level. In Comparative Example 2, the content of the antistatic agent was large, the heat stability was inferior, a large amount of gas was generated, and the light diffusibility did not satisfy the required level. Comparative Example 3 was a case where the molar ratio (hydroxy group / carboxyl group) between the hydroxy group of the polyhydric alcohol and the carboxyl group of the fatty acid was less than 4, and the surface resistance did not satisfy the required level. In Comparative Example 4, the molar ratio of the hydroxy group of the polyhydric alcohol to the carboxyl group of the fatty acid (hydroxy group / carboxyl group) exceeds 8, and the thermal stability does not satisfy the required level, and a large amount of gas is generated. The required level was not met. In Comparative Example 5, the amount of the epoxy polymer having a glycidyl group was small, and the thermal stability and the amount of gas generated did not satisfy the required levels. In Comparative Example 6, the amount of the glycidyl group-containing epoxy polymer was large, and the gas generation amount did not satisfy the required level. In Comparative Example 7, the epoxy polymer was an alicyclic epoxy polymer having no glycidyl group, and the thermal stability, gas generation amount, and light diffusibility did not satisfy the required levels. In Comparative Example 8, the amount of the light diffusing agent was small, and the light diffusibility did not satisfy the required characteristics. In Comparative Example 9, the amount of the light diffusing agent was large, and the amount of gas generated and the light diffusibility did not satisfy the required levels.

A Resin plate B Light source γ Diffusivity

Claims (10)

  (A) 0.5 to 5 parts by weight of an ester compound (component B) composed of a polyhydric alcohol and a fatty acid with respect to 100 parts by weight of the polycarbonate resin (component A), (C) an epoxy polymer containing a glycidyl group ( C component) 0.003-0.5 part by weight and (D) light diffusing agent (D component) 0.05-15 part by weight, and the hydroxyl group of polyhydric alcohol and the carboxyl group of fatty acid in B component The antistatic polycarbonate resin composition having light diffusibility, wherein the molar ratio (hydroxy group / carboxyl group) is in the range of 4-8.   2. The antistatic polycarbonate having light diffusibility according to claim 1, wherein 0.005 to 1 part by weight of (E) phosphorus antioxidant (E component) is contained with respect to 100 parts by weight of component A. 3. Resin composition.   The antistatic polycarbonate resin composition having light diffusibility according to claim 2, wherein the E component is a phosphite-based antioxidant.   4. The antistatic polycarbonate resin composition having light diffusibility according to claim 1, wherein the polyhydric alcohol in component B is diglycerin.   The antistatic polycarbonate resin composition having light diffusibility according to any one of claims 1 to 4, wherein the component C is a copolymer containing glycidyl methacrylate.   Content of D component is 0.1-3 weight part, Antistatic polycarbonate resin composition which has a light diffusibility in any one of Claims 1-5 characterized by the above-mentioned.   The average particle diameter of D component is 1-30 micrometers, The antistatic polycarbonate resin composition which has the light diffusibility in any one of Claims 1-6 characterized by the above-mentioned.   The light diffusibility according to any one of claims 1 to 7, comprising 0.0001 to 1.0 part by weight of (F) a metal salt flame retardant (F component) with respect to 100 parts by weight of component A. An antistatic polycarbonate resin composition comprising:   The antistatic polycarbonate resin composition having light diffusibility according to claim 8, wherein the F component is a sulfonic acid metal salt flame retardant.   A molded article formed by molding the antistatic polycarbonate resin composition according to claim 1.

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