JP2012214660A - Emission flame retardant light-diffusing resin composition and resin plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emission flame retardant light-diffusing resin composition and a resin plate which emit light for a long time in a dark place, excel in a light diffusion property, and has the performance that has an excellent flame retardancy of V-0 or V-1 in the UL-94 standard in a flame-retardant aromatic polycarbonate resin composition in which a luminous material is applied/added as an expressed element of a main function.SOLUTION: The emission flame retardant light-diffusing resin composition includes: based on (A) 100 parts by weight of an aromatic polycarbonate (A component) in which the viscosity average molecular weight is 1.8×10-3.0×10and which has a bifurcation structure of the branching fraction of 0.5-1.5 mol%, (B) 0.005-1.0 part by weight of an organic alkali (earth) metal salt (B-1 component) and 0.10-2.0 parts by weight of a silicone compound having an aromatic group (B-2 component) as a flame retardant (B component); (C) 0.50-10 parts by weight of a luminous material (C component) in which D50 particle size is 1-30 μm; and (D) 0.05-5.0 parts by weight of a light diffusion agent (D component) consisting of an organic fine particle whose average particle diameter is 1-20 μm.

Description

  The present invention relates to a light emitting flame retardant light diffusing resin composition and a resin plate comprising a flame retardant aromatic polycarbonate resin composition to which a phosphorescent material is applied and added as an expression element of a main function. Specifically, a light-emitting flame-retardant light-diffusing resin composition and a resin plate that emit light for a long time in a dark place, have excellent light diffusibility, and have good flame retardancy of V-0 or V-1 according to UL-94 standards About.

  A phosphorescent material is a material that excites molecular energy when exposed to light from the outside, and uses the light that is emitted when the energy level is lowered and returned to the original level over time. Since it emits light over time, it is used for nighttime displays such as evacuation guidance signs and indicator lights. In recent years, in the event of a disaster such as a fire or an earthquake, the problem that the interior lighting is turned off and the evacuation route is lost has become apparent, and the introduction of new functional facilities using phosphorescent materials is being promoted regardless of domestic and overseas. In such applications, there is a demand for a material having flame retardancy that allows evacuation guidance without causing flame collapse in a disaster.

  On the other hand, aromatic polycarbonate resins are used in a wide range of industrial fields by simple and excellent processing methods such as injection molding and extrusion molding. Especially for applications that require high transparency in various lighting covers, protective covers for transmissive displays, etc., taking advantage of the high transparency of aromatic polycarbonate resin with high light transmittance and extremely low haze ratio. Widely used. In these applications, in recent years, attention has been paid to flame retardancy at the time of fire, and a resin plate having high flame retardancy in addition to the required characteristics is required. In particular, by laminating functional films, practical functions such as optical path control and light reflection prevention are imparted, and technological progress that satisfies various performance requirements is spreading.

  As a method for imparting flame retardancy to an aromatic polycarbonate resin containing a phosphorescent material, a method using flame retardancy inherently possessed by the polycarbonate resin has been proposed (Patent Documents 1 and 2). However, in these methods, when the thickness of the polycarbonate resin sheet is 5.0 mm or more, the flame retardancy can be maintained, but the transparency cannot be maintained, and a large amount of phosphorescent material or a large amount of acrylic resin should be used. Therefore, it has been found that high levels such as flame retardancy V-0 and V-1 cannot be maintained despite the high oxygen index. A resin composition comprising a polycarbonate resin and a phosphorescent agent, a silicone compound as a flame retardant, and a light diffusing agent has been proposed (Patent Document 3). However, this composition has a flame retardancy of V-2 level and was not a resin composition having high flame retardancy.

On the other hand, bromine-based compounds and phosphorus-based compounds have been used as a method for developing flame retardancy by adding flame retardants to polycarbonate resins. However, the generation of corrosive gases during molding, or product recycling Silicone compounds and the like have been proposed in place of the flame retardants listed above for the purpose of improving the properties. For example, a method in which an alkali (earth) metal salt of perfluoroalkyl sulfonate and an organosiloxane having an alkoxy group, a vinyl group and a phenyl group are blended with a polycarbonate resin (see Patent Document 4), and an alkali of perfluoroalkyl sulfonic acid with a polycarbonate resin. A method of blending a metal salt or an alkaline earth metal salt and an organopolysiloxane containing an organoxysilyl group bonded to a silicon atom via a divalent hydrocarbon group has been proposed (see Patent Document 5). In addition, a method of blending a specific petroleum heavy oil or pitch and a silicone compound into the resin component (see Patent Document 6), and a unit represented by the formula R ₂ SiO _1.0 in a non-silicone resin having an aromatic ring And a method of blending a silicone resin having a unit represented by RSiO _1.5 (R is a hydrocarbon group) and having a weight average molecular weight of 10,000 or more and 270,000 or less (see Patent Document 7). Yes. Further, specific examples are described for a resin composition comprising an aromatic polycarbonate resin and an organic alkali metal salt and poly (methyl hydrogen siloxane) (see Patent Document 8).

However, the above-described proposed polycarbonate resin composition has a problem in that the transparency is lowered and the suitability for lighting use is lowered.
In response to this, in recent years, a resin composition comprising an aromatic polycarbonate resin and an organic alkali metal salt and poly (phenylmethylhydrogensiloxane) (see Patent Document 9), a resin composition comprising a branched polycarbonate and an organic metal salt Compositions (see Patent Document 10), resin compositions (see Patent Documents 11 and 12) composed of a polycarbonate having a branched structure, an organic metal salt, and a specific siloxane compound have been proposed. However, these patent documents do not have a composition that is supposed to be used in combination with a phosphorescent material.

Japanese Patent Laid-Open No. 11-080530 Japanese Patent Laid-Open No. 11-012502 JP 2008-074952 A JP-A-6-306265 JP-A-6-336547 JP-A-9-169914 Japanese Patent Laid-Open No. 10-139964 Japanese Patent Publication No. 60-38419 JP 2003-147190 A Japanese Patent No. 3129374 Japanese Patent No. 3163596 JP 2007-031583 A

  An object of the present invention is to provide a flame retardant aromatic polycarbonate resin composition to which a phosphorescent material is applied and added as an expression element of the main function, which emits light for a long time in a dark place, has excellent light diffusibility, and is V-compliant with UL-94 standard. An object of the present invention is to provide a light emitting flame retardant light diffusing resin composition and a resin plate having the performance of having favorable flame retardancy of −0 or V-1.

  Means to solve the above problems are evacuation guide lights that can be used in an emergency such as an earthquake or fire by combining a resin with excellent flame retardancy, light diffusivity and rigidity and a phosphorescent material under optimum conditions. A light emitting flame retardant light diffusing resin composition and a resin plate are provided. In addition, it is a composition in which a light diffusing agent is added to a composition that uses a flame retardant composition and a phosphorescent agent in combination, and the knowledge that the initial luminance and light emission intensity are improved compared to the composition that does not add a light diffusing agent has not been obtained so far. It is a knowledge that should be done.

That is, according to the present invention,
1. (A) Viscosity average molecular weight 1.8 × 10 ^{4 to} 3.0 × 10 ⁴ and 100 parts by weight of aromatic polycarbonate (component A) having a branched structure with a branching rate of 0.5 to 1.5 mol%, (B) As a flame retardant (component B), an organic alkali (earth) metal salt (component B-1) 0.005 to 1.0 parts by weight and a silicone compound having an aromatic group (component B-2) 0. 10 to 2.0 parts by weight, (C) 0.550 to 10 parts by weight of phosphorescent material (C component) having a D50 particle size of 1 to 30 μm, and (D) organic fine particles having an average particle size of 1 to 20 μm A light-emitting flame-retardant light-diffusing resin composition containing 0.05 to 5.0 parts by weight of a light diffusing agent (component D).
2. 2. The light-emitting flame-retardant light-diffusing resin composition according to item 1 above, wherein the phosphorescent material (component C) has one end on the long wavelength side of 430 nm to 680 nm in the wavelength region of the emitted light.
3. 2. The light-emitting flame-retardant light-diffusing resin composition as described in 1 above, wherein the light diffusing agent (component D) is a silicone resin.
4). A light-emitting flame-retardant light-diffusing resin plate having a thickness of 1.0 to 5.0 mm, which is molded using the resin composition according to item 1 above.
5. The light emission according to item ⁴ above, wherein the light intensity emitted from the resin plate is 1 mcd / m ² or more after 60 minutes in the JIS Z9107 test and V-0 or V-1 flame retardancy in the UL-94 test. Flame retardant light diffusing resin plate.
6). 5. The light-emitting flame-retardant light-diffusing resin plate according to item 4, wherein an angle (diffusivity) having a light intensity of 50% with respect to the light intensity in front of the resin plate is in a range of 10 to 60 degrees.
7). The illumination cover which uses the light emission flame-retardant light diffusable resin plate of any one of the preceding clauses 4-6.
8). A transmissive display cover using the light-emitting flame-retardant light-diffusing resin plate according to any one of 4 to 6 above.
Is provided.

  The light-emitting flame retardant light diffusing resin composition of the present invention is excellent as an evacuation guide light in an emergency such as an earthquake or fire by combining a resin having excellent flame retardancy, light diffusibility and rigidity with a phosphorescent material. In order to provide a function, it can be used in applications such as lighting covers, signboards, and transmissive displays.

  The composition having excellent flame retardancy, light diffusibility, and rigidity comprises a branched aromatic polycarbonate resin having a branched nucleus structure, a silicone compound containing an organic alkali (earth) metal salt and an aromatic group. It is a molded article made of a resin composition having an excellent light diffusibility and containing a light diffusing agent, and has high flame retardancy and light diffusibility. In the present invention, the blending amount of the organic alkali (earth) metal salt and the silicone compound is limited to an optimum range to provide excellent flame retardancy, and the remarkable effect is exhibited by selecting the type of polycarbonate resin to be used. I let you. In the present invention, bromine-based flame retardants and phosphorus-based flame retardants, which are considered to have a high environmental load, are not used, and a level unmatched by conventional flame retardant technologies is found.

  In addition, it was found that the light diffusing resin plate of the present invention significantly increases the light emission time and the light emission intensity as compared with a transparent resin plate not containing a light diffusing agent in the composition. Since the light diffusing resin plate of the present invention has the above-mentioned performance, it is extremely useful for various industrial applications, and the industrial effect exerted by it is enormous.

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

Details of the present invention will be described below.
(Component A: aromatic polycarbonate resin)
The aromatic polycarbonate resin used as the component A of the present invention is an aromatic polycarbonate resin having a branched structure and a branching ratio of 0.5 to 1.5 mol%. If the branching ratio as the whole component A satisfies 0.5 to 1.5 mol%, a linear aromatic polycarbonate resin having no branching structure or a branching ratio of 0.5 to 1.5 mol% It may be a mixture with an aromatic polycarbonate resin having a branched structure outside the range.

  From the viewpoint of imparting more excellent flame retardancy, the component A preferably contains 20 to 100% by weight, preferably 70 to 100% by weight, of an aromatic polycarbonate resin having a branching ratio of 0.5 to 1.5 mol%. Is more preferable, and it is further preferable to include 100% by weight.

The branching ratio as the whole component A is 0.5 to 1.5 mol%, preferably 0.7 to 1.2 mol%, and more preferably 0.75 to 1.0 mol. The branching rate is the number of moles of the structural unit derived from the branching agent to the total number of moles of the structural unit derived from the dihydric phenol used for the production included in the entire resin (the number of moles of the structural unit derived from the branching agent / derived from the divalent phenol The total number of moles of structural units × 100 (expressed in mol%)), and the branching ratio can be measured by ¹ H-NMR measurement.

  When the branching ratio is low, satisfactory branching characteristics cannot be obtained, the melt tension is too low, and flame retardancy, particularly drip prevention, is hardly exhibited. On the other hand, if the branching ratio is high, the polymer is crosslinked and a gel is easily generated, and the impact resistance of the polymer is lowered. Further, when the branching rate is too high, the surface of the molded product tends to be cloudy.

The viscosity average molecular weight of the component A is in the range of 1.8 × 10 ^{4 to} 3.0 × 10 ⁴ , preferably in the range of 1.9 × 10 ^{4 to} 2.8 × 10 ⁴ , and 2.0 × 10 ^4. A range of ˜2.6 × 10 ⁴ is more preferable. If the viscosity average molecular weight exceeds 3.0 × 10 ⁴ , the melt tension may be too high and the moldability may be poor, and if the viscosity average molecular weight is less than 1.8 × 10 ⁴ , drip prevention when the molded piece is burned The effect may be insufficient, that is, the excellent flame retardancy of the present invention may not be exhibited.

In addition, the aromatic polycarbonate resin used as the component A of the present invention may be mixed with one or more aromatic polycarbonate resins having a branched structure so that the molecular weight satisfies the aforementioned preferable molecular weight range. . In this case, it is naturally possible to mix a polycarbonate resin having a branched structure whose viscosity average molecular weight is outside the above preferred molecular weight range. In addition, the viscosity average molecular weight as used in the field of this invention calculates | requires first using the Ostwald viscometer from the solution which melt | dissolved 0.7 g of polycarbonate resins in 20 ml of methylene chloride with the specific viscosity computed by following Formula,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M can be determined by inserting the determined specific viscosity according to the following equation.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The polycarbonate resin having a branched structure which is the component A of the present invention preferably has a structural viscosity index in the range of 1.6 to 2.0. More preferably, it is the range of 1.65-1.95, More preferably, it is the range of 1.8-1.9. A PC resin having a structural viscosity index exceeding 2.0 tends to leave distortion in a molded product (particularly a sheet) during molding. On the other hand, when the structural viscosity index is less than 1.6, drip is likely to occur and the flame retardancy may not be satisfied. The structural viscosity index is measured at a temperature of 300 ° C., a capillary size of 10.01 × 1.0 mm, and a piston speed range of 5 to 200 mm.

  The polycarbonate resin having a branched structure which is the component A of the present invention can be obtained by an interfacial polymerization reaction method using a dihydric phenol, a branching agent, monohydric phenols and phosgene in the presence of an organic solvent.

  Representative examples of the dihydric phenol used are 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4- Hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenyl Ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4 , 4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropylidene) Phenol, 1,1-bis (4-hydroxyphenyl) -4-isopropyl cyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide and the like. These may be used alone or in combination of two or more. Of these, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferable.

  Representative examples of tri- or higher-valent phenols (branching agents) used in the present invention include 1,1,1-tris (4-hydroxyphenyl) ethane, 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) benzene, 2,6- Bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, tetra (4-hydroxyphenyl) methane, trisphenol, bis (2,4-dihydroxylphenyl) ketone, phloroglucin, phloroglucid, isantine bisphenol, Examples include 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, and pyromellitic acid. These may be used alone or in combination of two or more. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane is preferable.

  The monohydric phenol (terminal stopper) used in the production of the polycarbonate resin having a branched structure which is the component A of the present invention may have any structure and is not particularly limited. For example, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, 4-hydroxybenzophenone, phenol and the like can be mentioned. These may be used alone or in combination of two or more. Of these, p-tert-butylphenol is preferable.

  That is, the polycarbonate resin having a branched structure which is the component A of the present invention is a structure in which the branched structure portion is derived from 1,1,1-tris (4-hydroxyphenyl) ethane, and the branched structure portion is excluded. The linear structure portion is preferably a structure derived from bisphenol A, and the terminal is preferably a structure derived from p-tert-butylphenol.

The branched polycarbonate resin which is the component A of the present invention is preferably produced by the following method.
That is, phosgene was blown into an alkaline aqueous solution in which a dihydric phenol compound and a branching agent were dissolved in the presence of an organic solvent to obtain a polycarbonate oligomer. It is the method characterized by making it superpose | polymerize.

  Further, as a reaction catalyst for promoting the reaction, for example, tertiary amine such as triethylamine, tributylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compound, quaternary phosphonium A catalyst such as a compound can also be used. The reaction catalyst is preferably 0.002 mol% or less, more preferably 0.001 mol% or less with respect to the dihydric phenol compound. In particular, the above reaction is preferably carried out without a catalyst. When it exceeds 0.002 mol%, the melt tension becomes too high with respect to the amount of the branching agent, or a gel is formed. In addition, the catalyst reacts with the chloroformate group to increase the number of thermally unstable urethane bonds, and the remaining catalyst increases the total N content in the branched polycarbonate resin, resulting in impact resistance and transparency. This is not preferable because the heat resistance is lowered. Therefore, it is particularly preferable to carry out the above reaction without a catalyst. At that time, the reaction temperature is usually preferably 0 to 40 ° C, more preferably 15 to 38 ° C. The reaction time is about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9.0 or more, more preferably 11.0 to 13.8.

  There is no particular limitation on the method of emulsifying the monohydric phenols after adding the above-mentioned interfacial polymerization reaction, but examples include a method of stirring with a stirrer or a method of adding an alkaline aqueous solution. There are simple stirring devices such as paddles, propellers, turbines or chi-type blades, high-speed stirrers such as homogenizers, mixers and homomixers, static mixers, colloid mills, orifice mixers, flow jet mixers, ultrasonic emulsifiers and the like. Of these, homomixers, static mixers and the like are preferably used in the polymerization without catalyst.

  Next, the branched polycarbonate resin organic solvent solution is washed, granulated, and dried to obtain the branched polycarbonate resin (powder) of the present invention. Further, the powder is melt extruded and pelletized to obtain a branched polycarbonate resin (pellet). Cleaning, granulation, drying and the like are not particularly limited, and known methods can be employed.

  In order to reduce the total Cl content in the polycarbonate resin having a branched structure, dichloromethane (methylene chloride), dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, dichloroethylene, chlorobenzene, used as a solvent during the reaction, It is necessary to remove chlorinated hydrocarbon solvents such as dichlorobenzene. For example, it is possible to sufficiently dry the polycarbonate resin powder and pellets having a branched structure.

  It is preferable from the viewpoint of environmental influence that the aromatic polycarbonate having a branched structure of the present invention is substantially free of halogen atoms. The phrase “substantially free of halogen atoms” means that the molecule does not contain halogen-substituted dihydric phenols, etc., and a trace amount of solvent (halogenated hydrocarbon) remaining in the above aromatic polycarbonate production method or carbonate precursor Not even the body.

(B-1 component: organic alkali (earth) metal salt)
As the organic alkali (earth) metal salt used as the B-1 component of the present invention, various metal salts conventionally used for flame-retarding polycarbonate resins can be used. List alkali (earth) metal salts of acids, alkali (earth) metal salts of aromatic imides, alkali (earth) metal salts of sulfate esters, and alkali (earth) metal salts of phosphoric acid partial esters Can do. (Here, the notation of alkali (earth) metal salt is used to include both alkali metal salts and alkaline earth metal salts). These are not only used alone but also used in combination of two or more. It is also possible to do. The metal constituting the organic alkali (earth) metal salt is an alkali metal or an alkaline earth metal, and more preferably an alkali metal. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, and barium, and lithium, sodium, and potassium are particularly preferable.

Examples of the alkali (earth) metal salt of the organic sulfonic acid include an alkali (earth) metal salt of an aliphatic sulfonic acid and an alkali (earth) metal salt of an aromatic sulfonic acid.
Preferred examples of the alkali (earth) metal salt of the aliphatic sulfonic acid include an alkali (earth) metal salt of an alkyl sulfonate, and a part of the alkyl group of the alkali (earth) metal salt of the alkyl sulfonate is a fluorine atom. And alkali (earth) metal salts of sulfonates substituted with, and alkali (earth) metal salts of perfluoroalkyl sulfonates, and these can be used alone or in combination of two or more.

  Preferred examples of the alkali (earth) metal salt of alkyl sulfonate include methane sulfonate, ethane sulfonate, propane sulfonate, butane sulfonate, methyl butane sulfonate, hexane sulfonate, heptane sulfone. Examples thereof include acid salts and octane sulfonates, and these can be used alone or in combination of two or more. In addition, a metal salt in which a part of the alkyl group is substituted with a fluorine atom can also be mentioned.

  On the other hand, preferred examples of alkali (earth) metal salts of perfluoroalkyl sulfonate include perfluoromethane sulfonate, perfluoroethane sulfonate, perfluoropropane sulfonate, perfluorobutane sulfonate, perfluoro Examples include methylbutane sulfonate, perfluorohexane sulfonate, perfluoroheptane sulfonate, and perfluorooctane sulfonate, and those having 1 to 8 carbon atoms are particularly preferable. These can be used alone or in combination of two or more.

  Of these, the alkali metal salt of perfluoroalkylsulfonic acid is most preferable. Among these alkali metals, rubidium and cesium are suitable when the demand for flame retardancy is higher, but these are not versatile and difficult to purify, resulting in disadvantages in terms of cost. There is. On the other hand, although it is advantageous in terms of cost, lithium and sodium may be disadvantageous in terms of flame retardancy. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, but perfluoroalkylsulfonic acid potassium salt 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.

  Specific examples of alkali metal perfluoroalkyl sulfonates include potassium trifluoromethane sulfonate, potassium perfluorobutane sulfonate, potassium perfluorohexane sulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethane sulfonate, perfluoro Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonate Cesium, cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perf Oro hexane sulfonate rubidium, and these may be used in combination of at least one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

  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.

  Monomer or polymer aromatic sulfite alkali (earth) metal salts of aromatic sulfides are described in JP-A-50-98539, for example, disodium diphenyl sulfide-4,4′-disulfonate. And dipotassium diphenyl sulfide-4,4′-disulfonate.

  Examples of sulfonic acid alkali (earth) metal salts of aromatic carboxylic acids and esters are described in JP-A No. 50-98540, for example, potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, polyethylene terephthalate. And polysodium acid polysulfonate.

  Monomeric or polymeric aromatic ether sulfonate alkali (earth) metal salts are described in JP-A-50-98542, for example, 1-methoxynaphthalene-4-sulfonate calcium, 4- Disodium dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate, polysodium poly (1,3-phenylene oxide) polysulfonate, polysodium poly (1,4-phenylene oxide) polysulfonate And poly (2,6-diphenylphenylene oxide) polypotassium polysulfonate, poly (2-fluoro-6-butylphenylene oxide) lithium polysulfonate, and the like.

  Examples of alkali (earth) metal sulfonates of aromatic sulfonates are described in JP-A No. 50-98544, and examples thereof include potassium sulfonate of benzene sulfonate.

  Monomeric or polymeric aromatic (earth) metal sulfonates are described in JP-A No. 50-98546, for example, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, Examples include dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, and calcium biphenyl-3,3′-disulfonate.

  Monomeric or polymeric aromatic sulfonesulfonic acid alkali (earth) metal salts are described in JP-A-52-54746, for example, sodium diphenylsulfone-3-sulfonate, diphenylsulfone-3- Examples include potassium sulfonate, dipotassium diphenyl-3,3′-disulfonate, dipotassium diphenylsulfone-3,4′-disulfonate, and the like.

  Examples of alkali sulfonate alkali (earth) metal salts of aromatic ketones are described in JP-A No. 50-98547, for example, α, α, α-trifluoroacetophenone-4-sulfonic acid sodium salt, benzophenone-3 , 3'-disulfonic acid dipotassium.

  Heterocyclic sulfonic acid alkali (earth) metal salts are described in JP-A-50-116542, for example, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate. Thiophene-2,5-disulfonate calcium, sodium benzothiophenesulfonate, and the like.

  Examples of the alkali (earth) metal sulfonate of aromatic sulfoxide are described in JP-A-52-54745, and examples thereof include potassium diphenyl sulfoxide-4-sulfonate.

  Examples of the condensate obtained by methylene bond of alkali (earth) metal salt of aromatic sulfonate include formalin condensate of sodium naphthalene sulfonate and formalin condensate of sodium anthracene sulfonate.

  Examples of the alkali (earth) metal salt of the sulfate ester include, in particular, alkali (earth) metal salts of sulfate esters 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 ester of palmitic acid monoglyceride, stearic acid monoglyceride sulfate and the like. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate.

  Specific examples of the alkali (earth) metal salt of the phosphoric acid partial ester include bis (2,6-dibromo-4-cumylphenyl) phosphoric acid, bis (4-cumylphenyl) phosphoric acid, and bis (2,4,6). Alkali (earth) such as bis (2,4-dibromophenyl) phosphoric acid, bis (4-bromophenyl) phosphoric acid, diphenylphosphoric acid, bis (4-tert-butylphenyl) phosphoric acid ) Metal salts can be mentioned.

  Examples of the alkali (earth) metal salt of the aromatic imide include saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonamide (in other words, di (p-toluenesulfone) imide), N- (N Examples include '-benzylaminocarbonyl) sulfanilimide, and alkali (earth) metal salts such as N- (phenylcarboxyl) sulfanilimide and bis (diphenylphosphoric acid) imide.

  Among these, preferable components are selected from the group consisting of alkali (earth) metal salts of perfluoroalkyl sulfonates, alkali (earth) metal aromatic sulfonates, and alkali (earth) metal salts of aromatic imides. Among them, potassium perfluorobutanesulfonate, sodium perfluorobutanesulfonate, diphenylsulfone sulfonate represented by the formula (4), di (p-toluenesulfone) imide One or more compounds selected from the group consisting of potassium salt and sodium salt of di (p-toluenesulfone) imide are more preferred. Most preferred is potassium perfluorobutane sulfonate.

［式中、ｎは０〜３を表し、ＭはＫあるいはＮａを表す。］

[Wherein n represents 0 to 3, and M represents K or Na. ]

  The amount of the component B-1 contained in the aromatic polycarbonate resin composition used in the present invention is 0.005 to 1.0 part by weight with respect to 100 parts by weight of the aromatic polycarbonate resin (component A), Preferably it is 0.006-0.5 weight part, More preferably, it is 0.007-0.3 weight part, More preferably, it is 0.008-0.1 weight part, Most preferably, it is 0.01 ~ 0.05 parts by weight. When the content of the B-1 component is more than 1.0 part by weight, not only the transparency, which is a feature of the present invention, is impaired, but also in some cases, the resin is decomposed during molding and the flame retardancy is decreased. Direction. If the amount added is less than 0.005 parts by weight, the flame retardancy becomes insufficient and the flame retardancy that is the object of the present invention is not exhibited.

(B-2 component: silicone compound)
The silicone compound used as the B-2 component of the present invention is not particularly limited as long as the flame retardancy and transparency as the object of the present invention can be obtained, but is a silicone compound having an aromatic group, and further at 25 ° C. It is preferable that the viscosity is 300 cSt or less. As the viscosity increases, the transparency of the molded product decreases. Furthermore, in order for the B-2 component silicone compound to efficiently exhibit a flame retardant effect, the dispersed state in the combustion process is important. Viscosity is an important factor that determines the dispersion state. This is because if the silicone compound is too volatile during the combustion process, that is, if the viscosity of the silicone compound is too low, the silicone remaining in the system at the time of combustion is dilute. From this viewpoint considered to be difficult to form a structure, the viscosity at 25 ° C. is more preferably 10 to 300 cSt, still more preferably 15 to 200 cSt, and most preferably 20 to 170 cSt.

  The aromatic group of the B-2 component is bonded to the silicone atom, which improves compatibility with the polycarbonate resin and contributes to maintaining transparency, and is advantageous for forming a carbonized film during combustion. Therefore, it also contributes to the development of flame retardant effect. When it does not have an aromatic group, it tends to be difficult to obtain transparency of the molded product and to obtain high flame retardancy.

（式（５）中、Ｘはそれぞれ独立にＯＨ基、ヘテロ原子含有官能基を有しても良い炭素数１〜２０の炭化水素基を示す。ｎは０〜５の整数を表わす。さらに式（５）中においてｎが２以上の場合はそれぞれ互いに異なる種類のＸを取ることができる。）
（３）平均重合度が３〜１５０
であるシリコーン化合物の中から選択される少なくとも一種以上のシリコーン化合物である。 The silicone compound used as the B-2 component of the present invention is preferably a silicone compound containing a Si-H group. In particular, a silicone compound containing a Si—H group and an aromatic group in the molecule,
(1) The amount of Si—H group contained (Si—H amount) is 0.1 to 1.2 mol / 100 g.
(2) The ratio (aromatic group amount) in which the aromatic group represented by the following formula (5) is contained is 10 to 70% by weight, and

(In formula (5), each X independently represents an OH group or a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom-containing functional group. N represents an integer of 0 to 5. (5) In the case where n is 2 or more, different types of X can be taken.
(3) Average polymerization degree is 3 to 150
And at least one silicone compound selected from silicone compounds.

  More preferably, as the Si—H group-containing unit, at least selected from silicone compounds containing a structural unit represented by at least one of the structural units represented by the following formulas (6) and (7): One or more silicone compounds.

（式（６）および式（７）中、Ｚ^１〜Ｚ^３はそれぞれ独立に水素原子、ヘテロ原子含有官能基を有しても良い炭素数１〜２０の炭化水素基、または下記式（８）で示される化合物を示す。α１〜α３はそれぞれ独立に０または１を表わす。ｍ１は０もしくは１以上の整数を表わす。さらに式（８）中においてｍ１が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (6) and formula (7), Z ^{1 to} Z ³ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom-containing functional group, or the following formula (8 Α1 to α3 each independently represents 0 or 1. m1 represents 0 or an integer of 1 or more, and each repeating unit in the case where m1 is 2 or more in formula (8) (You can take multiple repeating units that are different from each other.)

（式（８）中、Ｚ^４〜Ｚ^８はそれぞれ独立に水素原子、ヘテロ原子含有官能基を有しても良い炭素数１〜２０の炭化水素基を示す。α４〜α８はそれぞれ独立に０または１を表わす。ｍ２は０もしくは１以上の整数を表わす。さらに式（８）中においてｍ２が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (8), Z ^{4 to} Z ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom-containing functional group. Α 4 to α 8 are each independently 0. Or represents 1. m2 represents 0 or an integer greater than or equal to 1. Further, in the formula (8), when m2 is 2 or more, the repeating unit may take a plurality of different repeating units.

  More preferably, when M is a monofunctional siloxane unit, D is a bifunctional siloxane unit, and T is a trifunctional siloxane unit, the silicone compound is composed of MD units or MDT units.

The structural unit Z ^{1 to} Z ^{8 represented} by the above formulas (6), (7) and (8), and the hetero atom-containing functional group in X of the formula (5) may have 1 to 20 carbon atoms. Hydrocarbon groups include methyl groups, ethyl groups, propyl groups, butyl groups, hexyl groups, decyl groups and other alkyl groups, cyclohexyl groups such as cycloalkyl groups, vinyl groups, allyl groups and other alkenyl groups, phenyl groups, and tolyl groups. An aryl group such as a group and an aralkyl group can be exemplified, and these groups may contain various functional groups such as an epoxy group, a carboxyl group, a carboxylic anhydride group, an amino group, and a mercapto group. More preferably, it is a C1-C8 alkyl group, an alkenyl group, or an aryl group, and especially a C1-C4 alkyl group, such as a methyl group, an ethyl group, and a propyl group, a vinyl group, or a phenyl group is preferable.

  Among the structural units represented by the formulas (6) and (7), when the silicone compound includes at least one structural unit represented by the formula, when it has a plurality of repeating units of siloxane bonds, they are randomly copolymerized. Any of block copolymerization and tapered copolymerization can be employed.

  In the present invention, it is preferable that the amount of Si—H in the silicone compound be in the range of 0.1 to 1.2 mol / 100 g for the silicone compound containing the Si—H group preferred as the B-2 component. When the Si—H amount is in the range of 0.1 to 1.2 mol / 100 g, formation of a silicone structure is facilitated during combustion. More preferred is a silicone compound having a Si-H amount in the range of 0.1 to 1.0 mol / 100 g, most preferably in the range of 0.2 to 0.6 mol / 100 g. When the amount of Si—H is small, it is difficult to form a silicone structure, and when the amount of Si—H is large, the thermal stability of the composition is lowered. Here, the silicone structure refers to a network structure formed by a reaction between silicone compounds or a reaction between a resin and silicone.

The Si—H group amount referred to here means the number of moles of the Si—H structure contained per 100 g of the silicone compound. This is the volume of hydrogen gas generated per unit weight of the silicone compound by the alkali decomposition method. Can be determined by measuring. For example, when 122 ml of hydrogen gas is generated per 1 g of the silicone compound at 25 ° C., the Si—H amount is 0.5 mol / 100 g according to the following formula.
122 × 273 / (273 + 25) ÷ 22400 × 100≈0.5

  On the other hand, in a resin composition in which a silicone compound is blended with an aromatic polycarbonate resin (component A), in order to suppress the white turbidity of a molded product or a decrease in transparency due to wet heat treatment, as described above, the dispersion state of the silicone compound is is important. When the silicone compound is unevenly distributed, the resin composition itself becomes cloudy, and further, peeling occurs on the surface of the molded product, or the silicone compound migrates during the wet heat treatment and is unevenly distributed to reduce transparency. This is because it is difficult to obtain a molded article having good properties. Important factors that determine the dispersion state include the amount of aromatic groups in the silicone compound and the average degree of polymerization. In particular, the average degree of polymerization is important in a transparent resin composition.

  From this viewpoint, the amount of aromatic group in the silicone compound is preferably 10 to 70% by weight as the silicone compound used in the present invention. More preferred is a silicone compound having an aromatic group content in the range of 15 to 60% by weight, most preferably in the range of 25 to 55% by weight. If the amount of the aromatic group in the silicone compound is less than 10% by weight, the silicone compound is unevenly distributed, resulting in poor dispersion, and it may be difficult to obtain a molded article having good transparency. If the amount of the aromatic group is more than 70% by weight, the molecular rigidity of the silicone compound itself is increased, and therefore it is unevenly distributed and poorly dispersed, and it may be difficult to obtain a molded product with good transparency.

Here, the amount of the aromatic group means the ratio of the aromatic group represented by the above-described formula (5) in the silicone compound, and can be obtained by the following calculation formula.
Aromatic group amount = [A / M] x 100 (wt%)
Here, A and M in the above formula represent the following numerical values, respectively.
A = total molecular weight of all aromatic group moieties represented by formula (5) contained in one molecule of the silicone compound M = molecular weight of the silicone compound

  Further, the silicone compound used as the B-2 component of the present invention preferably has a refractive index at 25 ° C. in the range of 1.40 to 1.60. More preferred is a silicone compound having a refractive index in the range of 1.42 to 1.59, and most preferred is a range of 1.44 to 1.59. When the refractive index is within the above range, the silicone compound is finely dispersed in the aromatic polycarbonate, thereby providing a resin composition with less white turbidity and good dyeability.

  Furthermore, the silicone compound used as the B-2 component of the present invention preferably has a volatilization amount of 18% or less by a heat loss method at 105 ° C./3 hours. More preferably, the silicone compound has a volatilization amount of 10% or less. When the volatilization amount is larger than 18%, there is a problem that the amount of the volatile matter from the resin increases when the resin composition of the present invention is extruded and pelletized, and more bubbles are generated in the molded product. There is a problem.

  The silicone compound used as the component B-2 may be linear or branched as long as the above conditions are satisfied, and the Si—H group may be a side in the molecular structure. It is possible to use various compounds having any of a chain, a terminal, a branch point, or a plurality of sites.

In general, the structure of a silicone compound containing a Si—H group in the molecule is constituted by arbitrarily combining the following four types of siloxane units.
M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 , (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _{1/2 and} other monofunctional siloxane units D unit: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO, etc. Unit T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) SiO _3/2 trifunctional siloxane units Q units etc.: 4 represented by SiO ₂ functional siloxane Unit

Specifically, the structure of the silicone compound containing a Si—H group used in the present invention is expressed as D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _{m D n T p, M m} D n Q q, M m T p Q q, M m D n T p Q q, D n T p, D n Q q, include _{D n} T p _{Q q.} Among these, preferable structures of the silicone compound are M _m D _n , M _m T _p , M _m D _n T _p , and M _m D _n Q _q , and more preferable structures are M _m D _n or M _m D _n. T _p .
(The coefficients m, n, p, q in the above formula are integers representing the degree of polymerization of each siloxane unit. Also, if any of m, n, p, q is a numerical value of 2 or more, the coefficient The siloxane units with can be two or more siloxane units having different hydrocarbon groups having 1 to 20 carbon atoms which may have a hydrogen atom or a hetero atom-containing functional group.

Here, the sum of the coefficients in each characteristic formula is the average degree of polymerization of the silicone compound. In this invention, it is preferable to make this average degree of polymerization into the range of 3-150, More preferably, it is the range of 4-80, More preferably, it is the range of 5-60. When the degree of polymerization is less than 3, the volatility of the silicone compound itself is increased, so that there is a problem that the volatile content from the resin tends to increase during processing of the resin composition containing the silicone compound. If the degree of polymerization is greater than 150, the flame retardancy and transparency of the resin composition containing this silicone compound tends to be insufficient.
In addition, said silicone compound may be used independently, respectively and may be used in combination of 2 or more type.

  Such a silicone compound having a Si—H bond can be produced by a method known per se. For example, the target product can be obtained by cohydrolyzing the corresponding organochlorosilanes according to the structure of the target silicone compound and removing by-product hydrochloric acid and low-boiling components. Further, a silicone oil having a C1-C20 hydrocarbon group that may have a Si-H bond, an aromatic group represented by the formula (5), or other heteroatom-containing functional group in the molecule, or a cyclic siloxane Or alkoxysilanes as starting materials, use an acid catalyst such as hydrochloric acid, sulfuric acid, methanesulfonic acid, etc., and optionally add water for hydrolysis to advance the polymerization reaction before use The target silicone compound can be obtained by removing the acid catalyst and the low boiling point in the same manner.

Furthermore, the silicone compound containing a Si-H group is a siloxane unit represented by the following structural formula M, M ^H , D, D ^H , D ^{φ 2} , T, T ^φ (where M: (CH ₃ ) ₃ SiO _{1 / 2} ^MH : H (CH ₃ ) ₂ SiO _1/2 D: (CH ₃ ) ₂ SiOD ^H : H (CH ₃ ) SiOD ^{φ 2} : (C ₆ H ₅ ) ₂ SiT: (CH ₃ ) SiO _{3/2 ^{T φ: (C 6 H 5}} ) has a _{SiO 3/2),} the average number of each _m of the siloxane units having per _{molecule, m h, d, d h} , d p2, t, t p In this case, it is preferable to satisfy all of the following relational expressions.
2 ≦ m + m _h ≦ 40
0.35 ≦ d + d _h + d _p2 ≦ 148
0 ≦ t + t _p ≦ 38
0.35 ≦ m _h + d _h ≦ 110

  Outside this range, it becomes difficult to simultaneously achieve good flame retardancy and excellent transparency in the resin composition of the present invention, and in some cases, it becomes difficult to produce a silicone compound containing a Si—H group.

  Content of the silicone compound used as B-2 component of this invention is 0.10-2.0 weight part with respect to 100 weight part of aromatic polycarbonate resin (A component), Preferably it is 0.15- 1.8 parts by weight, more preferably 0.2 to 1.5 parts by weight, and most preferably 0.3 to 1.0 parts by weight. When the content is more than 2.0 parts by weight, the heat resistance of the resin is lowered or gas is easily generated during the extrusion process. When the content is less than 0.10 parts by weight, the flame retardancy is hardly exhibited.

(C component; phosphorescent material)
In the present invention, a phosphorescent material is used as the C component. The phosphorescent material (C component) used in the present invention is a phosphorescent material usually used as a synthetic resin phosphorescent material, and is a sulfide-based phosphorescent material such as CaS: Bi, CaSrS: Bi, ZnCdS: Cu, ZnS: Cu. Zinc sulfide-based phosphorescent material such as MaAlbOc, wherein M is composed of at least one metal element selected from calcium, strontium and barium, and europium, lanthanum, cerium, praseodymium as an activator for the compound It consists of at least one element selected from neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, ruthenium, manganese, tin, and bismuth. Aluminic acid based at 10 mol% or less Such compounds, and the like. From the viewpoint of hydrolyzability and afterglow characteristics, an aluminate compound is preferable, and a strontium aluminate compound using strontium as a metal element and europium or dysprosium as an activator is more preferable.

  Furthermore, it is a requirement that the phosphorescent material has a D50 particle size of 1 to 30 μm. More preferably, it is the range of 2-20 micrometers. The D50 particle size indicates a diameter in which the large side and the small side are equivalent when the powder is divided into two from a certain particle size. Those having a thickness of less than 1 μm are not preferable because they are difficult to manufacture and are not practical and difficult to obtain. On the other hand, those exceeding 30 μm are not preferable because optical properties and appearance are impaired. Furthermore, two or more types of phosphorescent materials having different average particle diameters, particle size distributions, and types may be used in combination, and those having two or more particle size distributions that are not uniform are used alone or in combination. Can also be used.

  As a compounding quantity of a phosphorescent material, it is 0.50-10 weight part with respect to 100 weight part of aromatic polycarbonate resin (A component), Preferably it is 0.6-5 weight part, More preferably, it is 0.8. 7 to 3 parts by weight. If the blending amount is less than 0.50 parts by weight, the light emission time becomes extremely short, which is not preferable. On the other hand, if it exceeds 10 parts by weight, the optical properties are impaired, and the extrudability is extremely deteriorated.

  As the absorption wavelength of the phosphorescent material, it is desirable that the absorption maximum value be in the range of 300 nm to 500 nm. This is because the wavelength of light that is easy for the human eye to catch is around 550 nm. As a characteristic of the phosphorescent material, the radiation maximum always shifts to the long wavelength side rather than the absorption maximum. This is because it becomes extremely difficult to visually recognize. In addition, the phosphorescent material (C component) preferably has one end on the long wavelength side (light emission maximum value) of 430 nm to 680 nm in the wavelength region of the emitted light.

(D component; light diffusing agent)
In the present invention, a light diffusing agent is used as the D component. The light diffusing agent (component D) used in the present invention is a light diffusing agent usually used as a light diffusing agent for synthetic resins, and is in the form of fine particles, such as polystyrene resin, (meth) acrylic resin, silicone resin, etc. And organic fine particles.

  Such organic fine particles are preferably cross-linked organic fine particles, which are at least partially cross-linked in the production process, and are not practically deformed in the process of processing the thermoplastic resin and maintain the fine particle state. . In other words, fine particles that do not melt into the thermoplastic resin even when heated to the molding temperature of the thermoplastic resin (for example, the molding temperature of the polycarbonate resin is about 350 ° C.) are more preferable, specifically, organic particles of a crosslinked silicone resin. . Particularly preferred specific examples include silicone resins having a crosslinked siloxane bond [for example, KMP-701, KMP-702, X52-1621 manufactured by Shin-Etsu Chemical Co., Ltd., and Tospearl 120 manufactured by Toshiba Silicone Co., Ltd.].

  The fine particle light diffusing agent has an average particle diameter of 1 to 20 μm, preferably 1.1 to 15 μm, and more preferably 1.2 to 11 μm. If the average particle size is less than 1.0 μm, sufficient light diffusibility cannot be obtained and surface luminescence is inferior. If it exceeds 20 μm, sufficient light diffusibility cannot be obtained and surface luminescence is inferior, and sufficient light diffusion is achieved. In order to obtain the effect, the blending amount is increased, the light transmittance is impaired, the luminance unevenness is increased, and further, the light emission luminance of the phosphorescent material is impaired. The average particle diameter of the light diffusing agent is a weight average particle diameter measured by a coal counter method. As the measuring instrument, Nikka Co., Ltd. particle number / particle size distribution analyzer MODEL Zm or the like can be used.

  The blending ratio of the aromatic polycarbonate resin and the light diffusing agent is 0.05 to 5.0 parts by weight, and 0.1 to 4.5 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin (component A). Is preferable, and 0.2 to 4.0 parts by weight is more preferable. When the blending amount of the light diffusing agent is less than 0.05 parts by weight, the light diffusibility is insufficient, and the characteristic brightness improvement and light emission sustaining performance which are characteristic cannot be obtained. On the other hand, if the blending amount of the light diffusing agent exceeds 5 parts by weight, the extrudability may be lowered, and the target performance may not be obtained.

<Other ingredients>
On the other hand, the resin composition of the present invention may be blended with other resins and fillers as long as the object of the present invention is not impaired, but many of the other resins and fillers are flame retardant or Since it impedes luminescence, the selection of the type and amount should be considered.

  Unless the purpose of the present invention is impaired, the resin composition of the present invention contains a thermoplastic resin other than the component A in order to improve the mechanical properties, chemical properties, or electrical properties of the molded product. Can be blended. The blending amount of the other thermoplastic resin varies depending on the type and purpose, but is usually preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight per 100 parts by weight of the aromatic polycarbonate resin (component A). Is appropriate.

  Other thermoplastic resins include, for example, general-purpose plastics represented by polyethylene resin, polypropylene resin, polyalkyl methacrylate resin, polyphenylene ether resin, polyacetal resin, polyamide resin, cyclic polyolefin resin, polyarylate resin (non-crystalline) And so-called super engineering plastics such as engineering plastics typified by polyarylate and liquid crystalline polyarylate), polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, and polyphenylene sulfide. . Furthermore, thermoplastic elastomers such as olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers can also be used.

  In the resin composition of the present invention, additives known per se can be blended in a small proportion for imparting various functions and improving properties to the molded product. These additives are used in usual amounts as long as the object of the present invention is not impaired.

  Examples of such additives include anti-drip agents (such as fluorine-containing polymers having fibril-forming ability), heat stabilizers, ultraviolet absorbers, light stabilizers, mold release agents, lubricants, sliding agents (such as PTFE particles), and colorants. (Pigments and dyes such as carbon black and titanium oxide), fluorescent whitening agents, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide) , Fine zinc oxide, etc.), impact modifiers typified by graft rubber, infrared absorbers or photochromic agents.

  In order to improve the thermal stability, antioxidant property, light stability (ultraviolet light stability) and releasability of the resin composition of the present invention, the additives used for these improvements in the aromatic polycarbonate resin are as follows. Advantageously used. Hereinafter, these additives will be specifically described.

  The resin composition of this invention can mix | blend a phosphorus containing stabilizer as a heat stabilizer. As the phosphorus-containing stabilizer, any of phosphite compounds, phosphonite compounds, and phosphate compounds can be used.

  Various phosphite compounds can be used. Specific examples include phosphite compounds represented by the following general formula (9), phosphite compounds represented by the following general formula (10), and phosphite compounds represented by the following general formula (11).

［式中Ｒ^８は、水素原子または炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基ないしアルカリール基、炭素数７〜３０のアラルキル基、またはこれらのハロ、アルキルチオ（アルキル基は炭素数１〜３０）またはヒドロキシ置換基を示し、３個のＲ^８は互いに同一または互いに異なるのいずれの場合も選択でき、また２価フェノール類から誘導されることにより環状構造も選択できる。］

[Wherein R ⁸ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a halo or alkylthio thereof (an alkyl group) Represents 1 to 30 carbon atoms) or a hydroxy substituent, and three R ⁸ can be selected from the same or different from each other, and a cyclic structure can be selected by being derived from dihydric phenols. ]

［式中Ｒ^９、Ｒ^１０はそれぞれ水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基ないしアルキルアリール基、炭素数７〜３０のアラルキル基、炭素数４〜２０のシクロアルキル基、炭素数１５〜２５の２−（４−オキシフェニル）プロピル置換アリール基を示す。なお、シクロアルキル基およびアリール基は、アルキル基で置換されていないもの、またはアルキル基で置換されているもののいずれも選択できる。］

[Wherein R ⁹ and R ¹⁰ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkylaryl group, an aralkyl group having 7 to 30 carbon atoms, and an alkyl group having 4 to 20 carbon atoms. A cycloalkyl group, a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms is shown. The cycloalkyl group and the aryl group can be selected from those not substituted with an alkyl group or those substituted with an alkyl group. ]

［式中Ｒ^１１、Ｒ^１２は炭素数１２〜１５のアルキル基である。なお、Ｒ^１１およびＲ^１２は互いに同一または互いに異なるのいずれの場合も選択できる。］で表わされるホスファイト化合物を挙げることができる。

[Wherein R ¹¹ and R ¹² are alkyl groups having 12 to 15 carbon atoms. Note that R ¹¹ and R ¹² can be selected to be the same or different from each other. The phosphite compound represented by this can be mentioned.

  Examples of the phosphonite compound include a phosphonite compound represented by the following general formula (12) and a phosphonite compound represented by the following general formula (13).

［式中、Ａｒ^１、Ａｒ^２は炭素数６〜２０のアリール基ないしアルキルアリール基、または炭素数１５〜２５の２−（４−オキシフェニル）プロピル置換アリール基を示し、４つのＡｒ^１は互いに同一、または互いに異なるいずれも選択できる。または２つのＡｒ^２は互いに同一、または互いに異なるいずれも選択できる。］

[In the ^formula, Ar 1, Ar ² represents a 2- (4-oxyphenyl) propyl-substituted aryl group of the aryl group or alkyl aryl group having 6 to 20 carbon atoms, or 15-25 carbon atoms, the four Ar ¹ Either the same or different from each other can be selected. Alternatively, ^two Ar ² can be selected to be the same or different from each other. ]

  Preferable specific examples of the phosphite compound represented by the general formula (9) include diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenylmono (Tridecyl) phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite are mentioned.

  Preferred specific examples of the phosphite compound represented by the general formula (10) include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, etc., preferably distearyl pentaerythritol diphosphite, Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite can be mentioned.Such phosphite compounds can be used alone or in combination of two or more.

  Preferable specific examples of the phosphite compound represented by the general formula (11) include 4,4'-isopropylidenediphenol tetratridecyl phosphite.

  Preferable specific examples of the phosphonite compound represented by the general formula (12) include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di). -N-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert) -Butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propyl) Phenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-n-butylphenyl) -4,4′-bifu Nylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylenedi Examples thereof include phosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite is preferred, and tetrakis ( 2,4-di-tert-butylphenyl) -biphenylenediphosphonite is more preferred. The tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferably a mixture of two or more, specifically tetrakis (2,4-di-tert-butylphenyl) -4,4. '-Biphenylenediphosphonite (E2-1 component), tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite (E2-2 component) and tetrakis (2,4- One kind or two or more kinds of di-tert-butylphenyl) -3,3′-biphenylenediphosphonite (component E2-3) can be used in combination, but these three kinds of mixtures are preferable. In the case of three kinds of mixtures, the mixing ratio is preferably in the range of 100: 37 to 64: 4 to 14 by weight ratio of E2-1 component, E2-2 component and E2-3 component, and 100: 40 to 60 : The range of 5-11 is more preferable.

  Preferable specific examples of the phosphonite compound represented by the general formula (13) include bis (2,4-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-n). -Butylphenyl) -3-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3 -Phenyl-phenylphosphonite bis (2,6-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, Bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butyl) Benzyl) -3-phenyl-phenylphosphonite and the like, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, bis (2,4-di-tert-butylphenyl) -phenyl-phenyl Phosphonite is more preferred. The bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more, specifically, bis (2,4-di-tert-butylphenyl) -4- One or two of phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite can be used in combination. It is a mixture. In the case of two kinds of mixtures, the mixing ratio is preferably in the range of 5: 1 to 4 by weight, and more preferably in the range of 5: 2 to 3.

  On the other hand, as phosphate compounds, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl Examples thereof include phosphate and diisopropyl phosphate, and trimethyl phosphate is preferable.

  Among the above phosphorus-containing heat stabilizers, more preferred compounds include compounds represented by the following general formulas (14) and (15).

（式（１４）中、Ｒ^１３およびＲ^１４は、それぞれ独立して炭素原子数１〜１２のアルキル基、シクロアルキル基、アリール基またはアラルキル基を示す。）

(In formula (14), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.)

（式（１５）中、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^２１、Ｒ^２２、およびＲ^２３はそれぞれ独立して水素原子、炭素原子数１〜１２のアルキル基、シクロアルキル基、アリール基またはアラルキル基を示し、Ｒ^１９は水素原子または炭素原子数１〜４のアルキル基を示し、およびＲ^２０は水素原子またはメチル基を示す。）

(In the formula (15), R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, An aryl group or an aralkyl group, R ¹⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ²⁰ represents a hydrogen atom or a methyl group.)

In the formula (14), R ¹³ and R ¹⁴ are preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. Specific examples of the compound represented by the formula (14) include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, and tris (di-n-butyl). Phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) Examples thereof include phosphite, and tris (2,6-di-tert-butylphenyl) phosphite is particularly preferable.

  Specific examples of the compound represented by the formula (15) include phosphites derived from 2,2′-methylenebis (4,6-di-tert-butylphenol) and 2,6-di-tert-butylphenol, 2 2,2'-methylenebis (4,6-di-tert-butylphenol) and phosphites derived from phenol, especially from 2,2'-methylenebis (4,6-di-tert-butylphenol) and phenol. Derived phosphites are preferred.

  In addition, the phosphorus compound of Formula (15) can be manufactured by a well-known method. For example, there is a method in which a bisphenol compound represented by the following general formula (16) is reacted with phosphorus trichloride to obtain a corresponding phosphoric acid chloride, and then it is reacted with a phenol represented by the following general formula (17). .

（式（１６）中、Ｒ^２４、Ｒ^２５、Ｒ^２６、およびＲ^２７はそれぞれ水素原子、炭素原子数１〜１２のアルキル基、シクロアルキル基、アリール基またはアラルキル基を示し、Ｒ^２８は水素原子または炭素原子数１〜４のアルキル基を示し、およびＲ^２９は水素原子またはメチル基を示す。）

(In the formula (16), R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ²⁸ represents hydrogen. And represents an atom or an alkyl group having 1 to 4 carbon atoms, and R ²⁹ represents a hydrogen atom or a methyl group.)

（式（１７）中、Ｒ^３０、Ｒ^３１、およびＲ^３２はそれぞれ水素原子、炭素原子数１〜１２のアルキル基、シクロアルキル基、アリール基またはアラルキル基を示す。）

(In the formula (17), R ³⁰ , R ³¹ and R ³² each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.)

  Specific examples of the compound of the general formula (16) include 2,2′-methylenebisphenol, 2,2′-methylenebis (4-methylphenol), 2,2′-methylenebis (6-methylphenol), 2, 2'-methylenebis (4,6-dimethylphenol), 2,2'-ethylidenebisphenol, 2,2'-ethylidenebis (4-methylphenol), 2,2'-isopropylidenebisphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4,6-di-tert-butylphenol), 2, 2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-dihydroxy-3,3'-di α-methylcyclohexyl) -5,5′-dimethylphenylmethane, 2,2′-methylenebis (6-α-methyl-benzyl-p-cresol), 2,2′-ethylidene-bis (4,6-di-) tert-butylphenol), 2,2-butylidene-bis (4-methyl-6-tert-butylphenol), and the like, and 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert- Butylphenol) and 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol) are preferred.

  On the other hand, specific examples of the compound of the general formula (17) include phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2-tert- Butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6 Examples include tert-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4,6-tri-tert-butylphenol, and 2,6-di-tert-butyl-4-s-butylphenol. And compounds having two or more alkyl substituents are preferred.

  Examples of the antioxidant that can be added to the resin composition of the present invention include phenolic antioxidants. The phenolic antioxidant can suppress discoloration when exposed to heat and exhibits a certain degree of effect on improving flame retardancy. Various types of such phenolic antioxidants can be used.

  Specific examples of such phenolic antioxidants include, for example, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3 , 5-Di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert- Butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-me Renbis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′-ethylidene-bis (4,6-di-tert- Butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3 -(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [ 2-tert-butyl-4-methyl 6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) fe Ru] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl} -2,4,8, 10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2, 2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4′-di-thiobis (2,6-di-) tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol), 2,4-bis (n-octylthio) -6- (4-hydroxy 3 ', 5'-di-tert-butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N , N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) ) Butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-) Hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3- Hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3 -(3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane etc. are mentioned and can be preferably used.

  More preferably, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl) -2'-hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane Further, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate is preferable.

  Also, a sulfur-containing antioxidant can be used as the antioxidant. It is particularly suitable when the resin composition is used for rotational molding or compression molding. Specific examples of such sulfur-containing antioxidants include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate. , Distearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetra (β-laurylthiopropionate) ester, bis [2-methyl-4 -(3-laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) and the like. be able to. More preferably, a pentaerythritol tetra ((beta) -lauryl thiopropionate) ester can be mentioned.

  The phosphorus-containing heat stabilizer, phenolic antioxidant, and sulfur-containing antioxidant listed above can be used alone or in combination of two or more. A phosphorus-containing stabilizer is more preferable, and it is particularly preferable that the phosphorus-containing heat stabilizer contains the compound of the general formula (14).

  The proportion of these stabilizers in the composition is 0.0001 to 1 for each of the phosphorus-containing stabilizer, phenol-based antioxidant, or sulfur-containing antioxidant per 100 parts by weight of the aromatic polycarbonate resin (component A). It is preferable that it is a weight part. More preferably, it is 0.0005-0.5 weight part, More preferably, it is 0.001-0.2 weight part.

  A release agent can be blended in the resin composition of the present invention as necessary. In the present invention, since it has flame retardancy by containing B component, it is possible to achieve good flame retardancy even when a release agent that usually has an adverse effect on flame retardancy is blended. Can do. As such a release agent, those known per se can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax or 1-alkene polymer may be used. These may be modified with a functional group-containing compound such as acid modification), silicone compound (Other than the component B of the present invention. For example, linear or cyclic polydimethylsiloxane oil, polymethylphenyl silicone oil, etc. are used. Those modified with a functional group-containing compound such as acid modification are also used. ), Fluorine compounds (fluorine oil typified by polyfluoroalkyl ether, etc.), paraffin wax, beeswax and the like. Among these, saturated fatty acid esters, linear or cyclic polydimethylsiloxane oil, polymethylphenyl silicone oil, and fluorine oil can be mentioned. Preferable mold release agents include saturated fatty acid esters. For example, monoglycerides such as stearic acid monoglyceride, polyglycerin fatty acid esters such as decaglycerin decastate and decaglycerin tetrastearate, and lower fatty acid esters such as stearic acid stearate. , Higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used. The content of the release agent is preferably 0.01 to 0.3 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin (component A).

  The resin composition of the present invention may be desired to contain an ultraviolet absorber. Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy. -4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2 '-Dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis ( 5-benzoyl-4-hydroxy 2-methoxyphenyl) benzophenone ultraviolet absorbers typified by methane and the like.

  Examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, and 2- (2′-hydroxy). -5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'- Di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-3′-dodecyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α'-dimethylbenzyl) phenylbenzotriazole, 2- [2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetraphthal Ruimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ' , 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2- Yl) phenol], methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-benzotriazole ultraviolet rays typified by condensation products with polyethylene glycol An absorbent can be mentioned.

  Further, examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxy-phenol, 2- (4,6-bis- (2,4 There may be mentioned hydroxyphenyltriazine compounds such as -dimethylphenyl-1,3,5-triazin-2-yl) -5-hexyloxy-phenol.

  A light stabilizer can also be mix | blended with the resin composition of this invention. Examples of such light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2n-butyl malonate, 1,2,3,4-butane Condensation product of carboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanedicarboxylic acid and 1,2,2,6,6-pentamethyl- A condensate of 4-piperidinol and tridecyl alcohol, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1, , 2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, poly {[ 6-morpholino-s-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4, 8,10-tetraoxaspiro [5 5] Condensate with undecane) diethanol, N, N′-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4) -Piperidyl) amino] -chloro-1,3,5-triazine condensate, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β , Β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol, polymethylpropyl 3-oxy- [4 Hindered amines represented by-(2,2,6,6-tetramethyl) piperidinyl] siloxane.

  The content of the ultraviolet absorber and the light stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 1 part by weight, per 100 parts by weight of the aromatic polycarbonate resin (component A).

  In addition, a blueing agent can be blended in the resin composition of the present invention in order to counteract the yellowishness based on the ultraviolet absorber and the like. Any bluing agent can be used without any problem as long as it is usually used for polycarbonate resin. In general, anthraquinone dyes are preferred because they are readily available. Specific examples of the bluing agent include the general name Solvent Violet 13 [CA. No. (Color Index No.) 60725; Trade names “Macrolex Violet B” manufactured by Bayer, “Diaresin Blue G” manufactured by Mitsubishi Chemical Corporation, “Sumiplast Violet B” manufactured by Sumitomo Chemical Co., Ltd.], general name Solvent Violet 31 [CA. No. 68210; Trade name “Diaresin Violet D” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Violet 33 [CA. No. 60725; trade name “Diaresin Blue J” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Blue 94 [CA. No. 61500; trade name “Diaresin Blue N” manufactured by Mitsubishi Chemical Corporation, generic name Solvent Violet 36 [CA. No. 68210; Trade name: “Macrolex Violet 3R” manufactured by Bayer, Inc., generic name: Solvent Blue 97 [trade name: “Macrolex Blue RR” manufactured by Bayer, Inc.], and generic name: Solvent Blue 45 [CA. No. 61110; trade name “Terrazol Blue RLS” manufactured by Sand Corp.] and the like, and Macrolex Blue RR, Macrolex Violet B and Terrazol Blue RLS are particularly preferable. The content of the bluing agent is preferably 0.000005 to 0.0010 parts by weight, more preferably 0.00001 to 0.0001 parts by weight per 100 parts by weight of the aromatic polycarbonate resin (component A).

  The resin composition of the present invention is excellent in anti-drip properties, but a normal anti-drip agent can be used in combination to further reinforce such performance. However, in the resin composition of the present invention, the blending amount is suitably 0.2 parts by weight or less, preferably 0.1 parts by weight or less, and preferably 0.08 parts by weight or less with respect to 100 parts by weight of component A in order not to impair such transparency. More preferred is less than or equal to parts by weight, and even more preferred is less than or equal to 0.05 parts by weight. Examples of such an anti-drip agent include a fluorine-containing polymer having a fibril forming ability. Polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is particularly preferable. The term “transparency” does not impair transparency, for example, to use PTFE in an amount that does not exceed 5% of the Haze of a 2 mm thick plate. PTFE having a fibril forming ability has a very high molecular weight, and tends to be bonded to each other by an external action such as shearing force to form a fiber. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight determined from the standard specific gravity. Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and transparency. . Commercially available products of PTFE in the mixed form include “Metablene A3000” (trade name), “Metablene A3700” (trade name), “Metablene A3750” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., and GE Specialty Chemicals “BLENDEX B449” (trade name) and the like.

<Manufacture of molded product made of resin composition>
In order to produce a molded article comprising the resin composition of the present invention, any method is adopted. For example, after thoroughly mixing the components A to D and optionally other components using premixing means such as a V-type blender, Henschel mixer, mechanochemical apparatus, extrusion mixer, etc., an extrusion granulator or Granulation can be performed by a briquetting machine or the like, and then a molded product can be manufactured by injection molding or extrusion molding. As another method, the components A to D and optionally other components are independently fed to a melt kneader represented by a vented twin-screw rudder, and after premixing a part of the A component and other components, A method of supplying to the melt-kneader independently of the remaining components, the component B is diluted and mixed with water or an organic solvent, and then supplied to the melt-kneader, or the diluted mixture is premixed with other components, and then the melt-kneader The method of supplying to is also mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt kneader.

In this invention, it uses suitably as a resin board (sheet | seat) shape | molded using this resin composition. The thickness of the resin plate is preferably 1.0 to 5.0 mm, more preferably 1.2 to 4.0 mm, and even more preferably 1.5 to 3.5 mm. When the thickness is in the above range, the object of the present invention can be easily achieved such as having excellent flame retardancy. The resin plate preferably has a light intensity emitted from the resin plate of 1 mcd / m ² or more after 60 minutes in the JIS Z9107 test. Furthermore, it is preferable to have flame retardancy of V-0 or V-1 in the UL-94 test.

  In the resin plate of the present invention, the angle (diffusivity) having a light intensity of 50% with respect to the light intensity at the front of the plate is preferably in the range of 10 to 60 degrees, more preferably in the range of 20 to 57 degrees, 30 A range of ˜54 degrees is more preferable. Within this range, a resin diffusion plate having sufficient light diffusibility is obtained.

  In addition, the surface of the resin plate can be shaped, and examples of the method include a method of producing a melt-extruded sheet using a shaping roll having a convex shape or a V shape. There is no particular limitation on the shape of the shaping.

Furthermore, various surface treatments can be performed on the molded product. Surface treatment includes decorative coating, hard coat, water / oil repellent coat, hydrophilic coat, UV absorbing coat, infrared absorbing coat, electromagnetic wave absorbing coat, heat generating coat, antistatic coat, antistatic coating, conductive coating, and meta coating. Various surface treatments such as rising (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying, etc.) can be performed. In particular, the resin plate is a laminate in which a layer (transparent conductive layer) having, for example, a UV cut function, an antistatic performance, an IR cut performance, and an electromagnetic wave cut performance is laminated on one side or / and both sides as required. Also good. As a method for obtaining a laminate, there are a method by coextrusion or a method in which a laminate film or a transfer foil is thermocompression bonded after melt extrusion.
These resin plates are suitably used for illumination covers or transmission type spray cover applications.

  The form of the present invention considered to be the best by the present inventors is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

  The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The following items were evaluated.

(I) Appearance Visual evaluation was performed from a distance of 50 cm on the resin plate obtained from each composition of the examples. Good appearance, ○, no occurrence of gas, etc. at the time of extrusion molding is observed, but △ is a surface with minute irregularities, and x is a surface quality deteriorated by gas at the time of extrusion molding .

(Ii) Flame retardancy Using the resin plate obtained in the examples, a vertical combustion test of UL-94 standard was performed to evaluate the grade. When the determination fails to satisfy any of the criteria of V-0, V-1, and V-2, “notV” is indicated.

(Iii) Diffusion degree The resin plate obtained from each composition of the examples was measured using a dispersity meter manufactured by Nippon Denshoku Industries Co., Ltd. The measuring method 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. .

(Iv) Light emission time A plate measuring 100 mm in length and 100 mm in width is cut out from the resin plate obtained from each composition of the examples, the intensity of the emitted light is measured in accordance with JIS Z9107 standard, and the time until it becomes less than 1 mcd / m ² Was measured. At this time, the time when the radiation time was 60 minutes or more was marked as ◯, and the time when it was less than 60 minutes was marked as x.

(V) Light Radiation Intensity A plate 100 mm long × 100 mm wide is cut out from the resin plate obtained from each composition of the example, and the radiant light intensity is measured according to JIS Z9107 standard. The percentages were compared numerically.

(Vi) Branching rate in aromatic polycarbonate resin having a branched structure
The branching rate (branching agent content) in the aromatic polycarbonate resin was measured using ¹ H-NMR (JNM-AL400 manufactured by JEOL).

(Vii) Viscosity average molecular weight of aromatic polycarbonate resin 0.7 g of aromatic polycarbonate resin was dissolved in 100 ml of methylene chloride, and the resulting solution was determined for specific viscosity at 20 ° C. using an Ostwald viscometer. The molecular weight was determined.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

[Example 1]
Aromatic polycarbonate resin having a branched structure (branch rate 0.9 mol%, viscosity average molecular weight 25,000) (component A) 100 parts by weight, perfluorobutanesulfonic acid potassium salt (component B-1) 0.05 parts by weight, Green phosphorescent material (component C) having a D50 particle size of 29 μm (G-300M SrAl ₂ O manufactured by Nemoto Special Chemical Co., Ltd.) containing 0.5 parts by weight of a silicone compound (component B-2) containing Si—H groups and aromatic groups ₄ : Eu, Dy) 1.0 part by weight, light diffusing agent (component D) having an average particle size of 1.9 μm (crosslinked silicone resin; KMP-702 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 part by weight with T Using a die extruder, melt extrusion was performed at an extruder temperature of 290 to 330 ° C. and a die temperature of 290 to 330 ° C. to obtain a resin plate (A) having a width of about 1100 mm and a thickness of 3 mm. The evaluation results of this resin plate are shown in Tables 1-8.

[Example 2]
In Example 1, a branched aromatic polycarbonate resin having a branching rate of 0.6 mol% was used as the component A, and a resin plate was obtained under the same conditions as in Example 1 except for that. The evaluation results of this resin plate are shown in Table 1.

[Example 3]
In Example 1, a branched aromatic polycarbonate resin having a branching ratio of 1.2 mol% was used as the component A, and a resin plate was obtained under the same conditions as in Example 1 except for that. The evaluation results of this resin plate are shown in Table 1.

[Comparative Example 1]
In Example 1, a branched aromatic polycarbonate resin having a branching rate of 0.4 mol% was used as the component A, and a resin plate was obtained under the same conditions as in Example 1 except for that. The evaluation results of this resin plate are shown in Table 1.

[Example 4]
In Example 1, the resin plate was obtained under the same conditions as in Example 1 except that the B-1 component was changed to 0.1 parts by weight. The evaluation results of this resin plate are shown in Table 2.

[Example 5]
In Example 1, the B-1 component was changed to 1.0 part by weight, and all other components were obtained under the same conditions as in Example 1. The evaluation results of this resin plate are shown in Table 2.

[Comparative Example 2]
In Example 1, the resin component was obtained under the same conditions as in Example 1 except that the B-1 component was changed to 0.004 parts by weight. The evaluation results of this resin plate are shown in Table 2.

[Comparative Example 3]
In Example 1, the B-1 component was changed to 1.2 parts by weight, and a resin plate was obtained under the same conditions as in Example 1 except for the rest. The evaluation results of this resin plate are shown in Table 2.

[Example 6]
In Example 1, the B-2 component was changed to 1.0 part by weight, and a resin plate was obtained under the same conditions as in Example 1 except for the rest. The evaluation results of this resin plate are shown in Table 3.

[Comparative Example 4]
In Example 1, the resin plate was obtained under the same conditions as in Example 1 except that the B-2 component was changed to 0.08 parts by weight. The evaluation results of this resin plate are shown in Table 3.

[Comparative Example 5]
In Example 1, the resin plate was obtained under the same conditions as in Example 1 except that the B-2 component was changed to 3.0 parts by weight. The evaluation results of this resin plate are shown in Table 3.

[Example 7]
In Example 1, the C component was changed to 0.50 parts by weight, and a resin plate was obtained under the same conditions as in Example 1 except for the rest. The evaluation results of this resin plate are shown in Tables 4 and 8.

[Example 8]
In Example 1, the C component was changed to 5.0 parts by weight, and everything else was the same as in Example 1 to obtain a resin plate. The evaluation results of this resin plate are shown in Table 4.

[Example 9]
In Example 1, the C component was changed to 10.0 parts by weight, and a resin plate was obtained under the same conditions as in Example 1 for all others. The evaluation results of this resin plate are shown in Table 4.

[Comparative Example 6]
In Example 1, the C component was changed to 0.30 part by weight, and a resin plate was obtained under the same conditions as in Example 1 except for the rest. The evaluation results of this resin plate are shown in Table 4.

[Comparative Example 7]
In Example 1, the C component was changed to 12.0 parts by weight, and all other components were obtained under the same conditions as in Example 1. The evaluation results of this resin plate are shown in Table 4.

[Example 10]
In Example 1, a green phosphorescent material (G-300F SrAl ₂ O ₄ : Eu, Dy, D50 particle size 17 μm, manufactured by Nemoto Special Chemical Co., Ltd.) is used as the C component, and the resin is used under the same conditions as in Example 1. I got a plate. The evaluation results of this resin plate are shown in Table 5.

[Example 11]
In Example 1, a green phosphorescent material (G-300FFS SrAl ₂ O ₄ : Eu, Dy, D50 particle size 3 μm, manufactured by Nemoto Special Chemical Co., Ltd.) is used as the C component, and the resin is used under the same conditions as in Example 1. I got a plate. The evaluation results of this resin plate are shown in Table 5.

[Example 12]
In Example 1, the D component was changed to 0.10 parts by weight, and the rest was obtained in the same manner as in Example 1 except that the resin plate was obtained. The evaluation results of this resin plate are shown in Table 6.

[Example 13]
In Example 1, the D component was changed to 2.0 parts by weight, and everything else was obtained under the same conditions as in Example 1. The evaluation results of this resin plate are shown in Table 6.

[Example 14]
In Example 1, the D component was changed to 5.0 parts by weight, and a resin plate was obtained under the same conditions as in Example 1 for all others. The evaluation results of this resin plate are shown in Table 6.

[Comparative Example 8]
In Example 1, the D component was changed to 0.04 parts by weight, and the rest was obtained in the same manner as in Example 1 except that the resin plate was obtained. The evaluation results of this resin plate are shown in Table 6.

[Comparative Example 9]
In Example 1, the D component was changed to 6.0 parts by weight, and everything else was the same as in Example 1 to obtain a resin plate. The evaluation results of this resin plate are shown in Table 6.

[Example 15]
In Example 1, 2.0 parts by weight of a light diffusing agent having an average particle diameter of 20 μm (cross-linked acrylic diffusing agent MBX-20 manufactured by Sekisui Plastics Industry Co., Ltd.) was added as the D component, and all the others were the same as in Example 1. A resin plate was obtained under the conditions. The evaluation results of this resin plate are shown in Table 7.

[Example 16]
In Example 1, 1.0 part by weight of a light diffusing agent (crosslinked silicone resin; X52-1621 manufactured by Shin-Etsu Chemical Co., Ltd.) having an average particle diameter of 5 μm was added as the D component, and all other conditions were the same as in Example 1. A resin plate was obtained. The evaluation results of this resin plate are shown in Table 7.

[Example 17]
In Example 1, the C component was changed to 2.0 parts by weight, and the rest was obtained in the same manner as in Example 1 except that the resin plate was obtained. The evaluation results of this resin plate are shown in Table 8.

[Comparative Example 10]
In Example 1, the D component was changed to 0 part by weight, and the rest was obtained in the same manner as in Example 1 except that the resin plate was obtained. The evaluation results of this resin plate are shown in Table 8.

[Comparative Example 11]
In Example 7, the resin component was obtained under the same conditions as in Example 7 except that the D component was changed to 0 part by weight. The evaluation results of this resin plate are shown in Table 8.

[Comparative Example 12]
In Example 17, the D component was changed to 0 part by weight, and everything else was the same as in Example 17 to obtain a resin plate. The evaluation results of this resin plate are shown in Table 8.

  In addition, the following were used for (A component), (B-1 component), (B-2 component) of a flame-retardant aromatic polycarbonate resin board (A).

(A component)
(1) Production method of aromatic polycarbonate resin having a branched structure (branching rate: 0.9 mol%, molecular weight: 25,000) 2340 parts of ion-exchanged water and 25% sodium hydroxide in a reactor equipped with a thermometer, stirrer and reflux condenser 947 parts of an aqueous solution and 0.7 part of hydrosulfite were added, and 710 parts of bisphenol A was dissolved under stirring (bisphenol A solution). Then, 2299 parts of methylene chloride, 112 parts of 48.5% aqueous sodium hydroxide solution, 14% concentration 38.1 parts (1.00 mol%) of an aqueous solution in which 1,1,1-tris (4-hydroxyphenyl) ethane was dissolved at a concentration of 25% was added to an aqueous sodium hydroxide solution, and 354 parts of phosgene were added at 15 to 25 ° C. The phosgenation reaction was carried out over about 90 minutes.
After completion of phosgenation, 219 parts of 11% strength p-tert-butylphenol in methylene chloride and 88 parts of 48.5% aqueous sodium hydroxide solution were added, stirring was stopped, and the mixture was allowed to stand for 10 minutes, followed by stirring. After 5 minutes of emulsification, the mixture was processed with a homomixer (Special Machine Industries Co., Ltd.) at a rotation speed of 1200 rpm and a bath frequency of 35 times to obtain a highly emulsified dope. The highly emulsified dope was reacted in a polymerization tank (with a stirrer) at a temperature of 35 ° C. for 3 hours under non-stirring conditions to complete the polymerization.
After completion of the reaction, 5728 parts of methylene chloride was added for dilution, the methylene chloride phase was separated from the reaction mixture, 5000 parts of ion-exchanged water was added to the separated methylene chloride phase and mixed with stirring, and the stirring was stopped. The phase and the organic phase were separated. Next, water washing was repeated until the conductivity of the aqueous phase was almost the same as that of ion-exchanged water to obtain a purified polycarbonate resin solution. Next, methylene chloride was evaporated at a liquid temperature of 75 ° C. with a 1000 L kneader in which 100 L of ion-exchanged water was added to the purified polycarbonate resin solution to obtain a granular material. 25 parts of the granular material and 75 parts of water were put into a hot water treatment tank equipped with a stirrer and stirred and mixed at a water temperature of 95 ° C. for 30 minutes.
Subsequently, the mixture of the granular material and water was separated by a centrifugal separator to obtain a granular material containing 0.5% by weight of methylene chloride and 45% by weight of water. Next, this granular material was continuously supplied at 50 kg / hr (in terms of polycarbonate resin) to a SUS316L conductive heat receiving groove type biaxial stirring continuous dryer controlled at 140 ° C., and the condition of an average drying time of 3 hours And dried to obtain a polycarbonate resin particle having a branched structure. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 25,000 and a branching ratio of 0.9 mol%.

(2) Process for producing aromatic polycarbonate resin having a branched structure (branch rate 0.6 mol%, molecular weight 25,200) 352 parts of phosgene, 1,1,1-tris (4 Except for changing to 26.7 parts (0.70 mol%) of an aqueous solution in which -hydroxyphenyl) ethane was dissolved at a concentration of 25%, and 206 parts of methylene chloride solution of 11% concentration of p-tert-butylphenol, It carried out similarly and obtained the polycarbonate resin granular material which has a branched structure. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 25200 and a branching rate of 0.6 mol%.

(3) Production method of aromatic polycarbonate resin having a branched structure (branch rate: 1.2 mol%, molecular weight: 20,200) 358 parts of phosgene and 1,1,1-tris (4 Except for changing to 53.3 parts (1.40 mol%) of an aqueous solution in which -hydroxyphenyl) ethane was dissolved at a concentration of 25%, and 276 parts of an 11% concentration of p-tert-butylphenol in methylene chloride, It carried out similarly and obtained the polycarbonate resin granular material which has a branched structure. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 20,200 and a branching ratio of 1.2 mol%.

(4) Production method of aromatic polycarbonate resin having a branched structure (branch rate 0.4 mol%, molecular weight 25,100) 352 parts of phosgene, 1,1,1-tris (4 Except for changing to 17.1 parts (0.45 mol%) of an aqueous solution in which -hydroxyphenyl) ethane was dissolved at a concentration of 25%, and 206 parts of methylene chloride solution of 11% concentration of p-tert-butylphenol, It carried out similarly and obtained the polycarbonate resin granular material which has a branched structure. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 25100 and a branching rate of 0.4 mol%.

(B-1 component)
Perfluorobutanesulfonic acid potassium salt (Megafac F-114P manufactured by Dainippon Ink, Inc.)

(B-2 component)
Manufacturing method of silicone compound containing Si-H group and aromatic group 301.9 g of water and 150 g of toluene were charged into a 1 L flask equipped with a stirrer, a cooling device, and a thermometer, and cooled to an internal temperature of 5 ° C. A mixture of trimethylchlorosilane (21.7 g), methyldichlorosilane (23.0 g), dimethyldichlorosilane (12.9) and diphenyldichlorosilane (76.0) was charged into the dropping funnel and dropped into the flask over 2 hours while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged for 4 hours with stirring at an internal temperature of 20 ° C., then left to stand to remove the separated hydrochloric acid aqueous layer, added with 10% aqueous sodium carbonate solution, stirred for 5 minutes and then left to stand. The separated aqueous layer was removed. Then, it wash | cleaned 3 times with ion-exchange water, and it confirmed that the toluene layer became neutral. The toluene solution was heated to an internal temperature of 120 ° C. under reduced pressure to remove toluene and low-boiling substances, and then insoluble materials were removed by filtration to obtain a silicone compound. This silicone compound had an Si—H group content of 0.21 mol / 100 g, an aromatic group content of 49% by weight, and an average degree of polymerization of 8.0.
Schematic formula of the obtained silicone compound M ₂ ^DH ₂ D ₁ D ^φ2 ₃
Each symbol represents the following siloxane unit, and the coefficient (subscript) of each symbol represents the number of siloxane units (degree of polymerization) in one molecule.
M: (CH ₃ ) ₃ SiO _{1/2
^{D H: H (CH 3)}} SiO
D: (CH ₃ ) ₂ SiO
D ^φ2 : (C ₆ H ₅ ) ₂ SiO

  The light-emitting flame-retardant light-diffusing resin composition of the present invention is useful for applications such as lighting covers, signboards, and transmissive displays.

A Resin plate B Light source γ Diffusivity

Claims (8)

(A) Viscosity average molecular weight 1.8 × 10 ^{4 to} 3.0 × 10 ⁴ and 100 parts by weight of aromatic polycarbonate (component A) having a branched structure with a branching rate of 0.5 to 1.5 mol%, (B) As a flame retardant (component B), an organic alkali (earth) metal salt (component B-1) 0.005 to 1.0 parts by weight and a silicone compound having an aromatic group (component B-2) 0. 10 to 2.0 parts by weight, (C) 0.550 to 10 parts by weight of phosphorescent material (C component) having a D50 particle size of 1 to 30 μm, and (D) organic fine particles having an average particle size of 1 to 20 μm A light-emitting flame-retardant light-diffusing resin composition containing 0.05 to 5.0 parts by weight of a light diffusing agent (component D).   The luminescent flame-retardant light diffusing resin composition according to claim 1, wherein the phosphorescent material (component C) has one end on the long wavelength side of 430 nm to 680 nm in the wavelength region of the emitted light.   The light diffusing flame retardant light diffusing resin composition according to claim 1, wherein the light diffusing agent (component D) is a silicone resin.   A light-emitting flame-retardant light-diffusing resin plate having a thickness of 1.0 to 5.0 mm, molded using the resin composition according to claim 1. The light intensity emitted from the resin plate is 1 mcd / m ² or more after 60 minutes in the JIS Z9107 test, and has flame retardancy of V-0 or V-1 in the UL-94 test. Luminescent flame retardant light diffusing resin plate.   5. The light-emitting flame-retardant light diffusing resin plate according to claim 4, wherein an angle (diffusivity) having a light intensity of 50% with respect to the light intensity in front of the resin plate is in a range of 10 to 60 degrees. .   The illumination cover which uses the light emission flame-retardant light diffusable resin plate of any one of Claims 4-6.   A transmissive display cover using the light-emitting flame-retardant light-diffusing resin plate according to any one of claims 4 to 6.

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