JP2015172150A - Black resin composition and black molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black resin composition and a black molded product that are excellent in low-temperature impact resistance, flowability, surface hardness, and heat resistance, and have jet-black appearance of a quality and transparency similar to a high-grade glass lacquer ware.SOLUTION: A black resin composition comprises a copolymer polycarbonate resin 100 pts.wt. in which the main repeating unit is a unit (A) represented by the following formula, a specific viscosity measured with methylene chloride solution at 20°C is 0.23-0.60, and a load deflection temperature is 80°C or more, and also comprises a colorant (component C) 0.01-5 pts.wt. and hindered amine photostabilizer (component D) 0.01-5 pts.wt based on the copolymer polycarbonate resin 100 pts.wt.

Description

  The present invention relates to a polycarbonate resin composition excellent in jetness and a resin molded product comprising the same. More specifically, it has excellent low-temperature impact resistance, weather resistance, scratch resistance, and heat resistance, and has a texture and transparency similar to a high-grade glass lacquer ware with a colorant added to a polycarbonate resin derived from a specific aliphatic dihydroxy structural unit. The present invention relates to a black resin composition having a jet black appearance and a black molded product.

  Polycarbonate resin is excellent in transparency, impact resistance, heat resistance, and dimensional stability, so as an engineering plastic, it can be used as an electrical / electronic / OA equipment casing and parts, automotive interior / exterior parts, furniture, and musical instruments. It is used in a wide range of fields such as miscellaneous goods. Polycarbonate resin, on the other hand, is a paint general test method described in JIS K5600-5-4-Part 5: Mechanical properties of coating film-Section 4: Pencil hardness measured in accordance with scratch hardness (pencil method) is 2B The surface is soft and easily damaged. In particular, it is represented by casings, interior panels, door handles, steering, car audio / car navigation frames, and shift knobs of electric / electronic / OA devices such as mobile phones, LCD TVs, speakers, portable game machines, and notebook computers. Automotive exterior parts such as automobile interiors, roof spoilers, and window garnishes, furniture, and musical instruments are required to have a texture and transparency that are similar to those of high-quality glass lacquerware. The scratches on the surface will cause a fatal appearance defect.

  As a method for improving the scratch resistance of a polycarbonate resin, it is generally known to impart jet blackness and scratch resistance by coating the resin surface. However, due to the wettability of the paint to the resin surface and the environmental conditions of the painting process, appearance defects such as pinholes, cracks, repellency, and yuzu skin (orange peel) occur and poor paint adhesion, resulting in a significant decrease in the yield of the painting process. However, productivity is inferior.

As a technique for improving the scratch resistance of a polycarbonate resin without painting, a method of laminating an acrylic resin film or sheet on the resin surface is known (for example, Patent Document 1). However, the acrylic resin has lower heat resistance than the polycarbonate resin and more easily absorbs water, so that the dimensional change due to temperature and humidity is large, and the final product is warped. Furthermore, the appearance distribution is caused by the film thickness distribution of the acrylic resin film or the sheet, and the jet black tone of the high-class feeling is impaired.
Therefore, it is known to use a resin composition obtained by adding a colorant to a copolymer polycarbonate resin (for example, Patent Document 2) excellent in scratch resistance, and a resin molded body. However, the copolymer polycarbonate resin has a problem that the impact resistance is greatly inferior, and has not been put into practical use.

Furthermore, the use of a resin composition in which PBT resin (polybutylene terephthalate) and AS resin (acrylonitrile-styrene) are mixed with polycarbonate resin in which carbon black, which is a black pigment, is dispersed improves surface hardness. However, when the impact modifier is added to compensate for this, there is a problem that jetness is lowered (for example, Patent Document 3).
In addition, a resin composition obtained by adding a colorant and a specific amount of a hindered amine stabilizer to a polycarbonate composed of a structural unit derived from isosorbide and cyclohexanedimethanol is excellent in weather resistance, impact resistance, and jet blackness. If the amount of isosorbide is reduced for the purpose of improving the surface impact property, heat resistance is reduced at the same time, so that there is a problem in practicality. (For example, Patent Document 4)
Therefore, it does not require painting, has excellent low temperature impact resistance, weather resistance, scratch resistance, heat resistance, black resin composition having a jet black appearance with a texture and transparency like high-quality lacquer ware, and black molding The goods are not present yet.

JP 2007-160892 A JP 2013-112781 A JP-A-11-106518 JP 2013-209585 A

  The object of the present invention is derived from a specific aliphatic dihydroxy structural unit having a jet-black appearance that has excellent low-temperature impact resistance, weather resistance, scratch resistance, and heat resistance, and has a texture and transparency similar to a high-class lacquer ware. Another object of the present invention is to provide a black resin composition obtained by adding a colorant to an aliphatic polycarbonate resin, and a black molded product.

As a result of intensive studies, the present inventors have found that a polycarbonate resin composed of isosorbide and a specific aliphatic dihydroxy component, a colorant, and a black colored resin composition composed of a hindered amine light stabilizer have low-temperature impact resistance. The present inventors have found that it is excellent in weather resistance, scratch resistance, and heat resistance, and have completed the present invention.
That is, according to the present invention, the object of the invention is achieved by the following.

で表される単位（Ａ）と下記式

（式中、Ｗは、炭素数８〜１２のアルキレン基を示す。）
で表される単位（Ｂ）を含み、単位（Ａ）と単位（Ｂ）とのモル比（Ａ／Ｂ）が８０／２０〜９５／５であり、２０℃の塩化メチレン溶液で測定された比粘度が０．２３〜０．６０、荷重たわみ温度が８０℃以上である共重合ポリカーボネート樹脂１００重量部に対して、着色剤（Ｃ成分）０．０１〜５重量部と、ヒンダードアミン系光安定剤（Ｄ成分）０．０１〜５重量部を含有する樹脂組成物であって、該樹脂組成物は下記（１）〜（４）の特性を満たすことを特徴とする黒色樹脂組成物。
（１）ＪＩＳ Ｋ５６００−５−４に則して測定された鉛筆硬度がＦ〜２Ｈである
（２）−２０℃の環境下においてＡＳＴＭ Ｄ３７６３に準拠した高速面衝撃試験の最大衝撃エネルギーが２０Ｊ以上であり、脆性破壊率が５０％以下である
（３）ＪＩＳ Ｚ８７４１に則して測定した入射受光角２０度における光沢度が７５以上９５以下であり、入射受光角６０度における光沢度が８０以上１００以下である
（４）上記樹脂組成物から成形された成形体（厚さ３ｍｍ）のＪＩＳ Ｚ８７２９に則して測定した明度（Ｌ＊）が３０以下である
２．着色剤（Ｃ成分）が有機染料であり、前記ポリカーボネート樹脂１００重量部に対して、０．０１〜１重量部を含有する前項１記載の黒色樹脂組成物。
３．光安定剤（Ｄ成分）がＮ−ＣＨ_３型ヒンダードアミン系光安定剤であり、前記ポリカーボネート樹脂１００重量部に対して、０．０１〜１重量部を含有する前項１記載の黒色樹脂組成物。
４．前項１〜３のいずれか１項に記載の黒色樹脂組成物を成形してなる黒色成形品。 1. The main repeating unit is the following formula

Unit (A) represented by the following formula

(In the formula, W represents an alkylene group having 8 to 12 carbon atoms.)
The molar ratio (A / B) of the unit (A) to the unit (B) is 80/20 to 95/5, and was measured with a 20 ° C. methylene chloride solution. With respect to 100 parts by weight of a copolymer polycarbonate resin having a specific viscosity of 0.23 to 0.60 and a deflection temperature under load of 80 ° C. or more, 0.01 to 5 parts by weight of a colorant (component C), and a hindered amine light stability A black resin composition comprising 0.01 to 5 parts by weight of an agent (D component), wherein the resin composition satisfies the following characteristics (1) to (4):
(1) The pencil hardness measured in accordance with JIS K5600-5-4 is F to 2H. (2) The maximum impact energy of a high-speed surface impact test according to ASTM D3763 is 20 J or more in an environment of -20 ° C. The brittle fracture rate is 50% or less. (3) The glossiness at an incident light reception angle of 20 degrees measured in accordance with JIS Z8741 is 75 or more and 95 or less, and the glossiness at an incident light reception angle of 60 degrees is 80 or more. (4) The lightness (L *) measured in accordance with JIS Z8729 of a molded body (thickness 3 mm) molded from the resin composition is 30 or less. The black resin composition according to item 1 above, wherein the colorant (component C) is an organic dye and contains 0.01 to 1 part by weight with respect to 100 parts by weight of the polycarbonate resin.
3. 2. The black resin composition according to item 1, wherein the light stabilizer (component D) is an N—CH ₃ type hindered amine light stabilizer and contains 0.01 to 1 part by weight with respect to 100 parts by weight of the polycarbonate resin.
4). The black molded product formed by shape | molding the black resin composition of any one of the preceding clauses 1-3.

  Since the black resin composition and the black molded product of the present invention have excellent jet blackness and are excellent in low-temperature impact resistance, weather resistance, scratch resistance, and heat resistance, they are used in electronic / electric / OA equipment exterior parts, automobiles. Applicable to applications that require high-grade appearance such as interior and exterior parts, furniture, and musical instruments. Therefore, the industrial effects that it plays are exceptional.

Hereinafter, the present invention will be described in detail.
<Polycarbonate resin>
In the polycarbonate resin of the present invention, the main repeating unit is composed of a unit (A) and a unit (B). The main repeating unit in the present invention is preferably a total of units (A) and (B) of 60 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, based on all repeating units. And particularly preferably 90 mol% or more.

(Unit (A))
The unit (A) in the present invention is derived from an aliphatic diol having an ether group, as shown in the formula (A).
In the formula (A), a diol having an ether bond among biomass resources is a material having high heat resistance and high pencil hardness.
Examples of the formula (A) include repeating units (A1), (A2) and (A3) represented by the following formulas having a stereoisomer relationship.

These are saccharide-derived ether diols that are also obtained from natural biomass and are one of the so-called renewable resources. The repeating units (A1), (A2) and (A3) are called isosorbide, isomannide and isoidide, respectively. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can be obtained by the same reaction except for the starting materials.
Among isosorbide, isomannide, and isoidide, a repeating unit derived from isosorbide (1,4; 3,6-dianhydro-D-sorbitol) is particularly preferable because of ease of production and heat resistance.

(Unit (B))
The unit (B) in the polycarbonate resin of the present invention is derived from an aliphatic diol having 8 to 12 carbon atoms as shown in the formula (B).
Examples of the aliphatic diol having 8 to 12 carbon atoms include 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2,4-diethyl-1,5- Examples include pentanediol and 2-methyl-1,8-octanediol, and 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol are preferable. -Nonanediol, 1,10-decanediol, and 1,12-dodecanediol are more preferable. Two or more of these may be used in combination.

(Other units)
The diol compound for deriving other copolymerization unit may be any of other aliphatic diol compounds, alicyclic diol compounds, and aromatic dihydroxy compounds. International Publication No. 2004/111106, International Publication No. Examples thereof include diol compounds described in the 2011/021720 pamphlet and oxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol.
Examples of other aliphatic diol compounds include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, and neopentyl. Examples include glycol and 3-methyl-1,5-pentanediol.

  Examples of the alicyclic diol compound include 2-methyl-1,3-cyclobutanediol, 2,4-dimethyl-1,3-cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2-ethyl-1,3-cyclobutanediol, 2,4-diethyl-1,3-cyclobutanediol, 2,2,4,4-tetraethyl-1,3-cyclobutanediol, 2-butyl-1,3-cyclobutane Diol, 2,4-dibutyl-1,3-cyclobutanediol, 2,2,4,4-tetrabutyl-1,3-cyclobutanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, adamantanediol, pentacycline Penta decane dimethanol, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-spiro [5.5] undecane.

  As aromatic dihydroxy compounds, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene (bisphenol M), 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1- Bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, bisphenol A, 2 , 2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (bisphenol AF) ) And 1,1-bis (4-hydroxyphenyl) decane.

(composition)
As for the polycarbonate resin of this invention, the main repeating unit contains a unit (A) and a unit (B), and those molar ratio (A / B) is 80 / 20-95 / 5. When the molar ratio (A / B) is 80/20 to 95/5, the pencil hardness increases, the heat resistance increases, and the low water absorption is excellent. The molar ratio of the unit (A) to the unit (B) is preferably 82/18 to 93/7, and more preferably 84/16 to 92/8. When the molar ratio (A / B) is smaller than 80/20, the heat resistance is low, and when the molar ratio (A / B) is larger than 95/5, the water absorption is high and the fluidity is low. Getting worse. The molar ratio (A / B) can be measured and calculated by proton NMR of JNM-AL400 manufactured by JEOL.

(Production method of polycarbonate resin)
The polycarbonate resin of the present invention is produced by a reaction means known per se for producing an ordinary polycarbonate resin, for example, a method of reacting a diol component with a carbonate precursor such as a carbonic acid diester. Next, basic means for these manufacturing methods will be briefly described.

  The transesterification reaction using a carbonic acid diester as a carbonate precursor is performed by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating with an inert gas atmosphere to distill the generated alcohol or phenols. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, you may add a terminal stopper, antioxidant, etc. as needed.

  Examples of the carbonic acid diester used in the transesterification include esters such as an aryl group having 6 to 12 carbon atoms and an aralkyl group which may be substituted. Specific examples include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate and m-cresyl carbonate. Of these, diphenyl carbonate is particularly preferred. The amount of diphenyl carbonate used is preferably 0.97 to 1.10 mol, more preferably 1.00 to 1.06 mol, per 1 mol of the total of dihydroxy compounds.

In the melt polymerization method, a polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal compounds.
As such compounds, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, quaternary ammonium hydroxides, and the like of alkali metals and alkaline earth metals are preferably used. It can be used alone or in combination.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, Sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphorus Examples include dilithium oxyhydrogen, disodium phenylphosphate, disodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, sodium salt of phenol, potassium salt, cesium salt, lithium salt and the like.
Alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, diacetate Barium and the like are exemplified.

  Examples of nitrogen-containing compounds include quaternary ammonium hydroxides having alkyl, aryl groups, etc., such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Can be mentioned. Further, tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole can be used. Moreover, bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate and the like are exemplified.

Examples of metal compounds include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds, and the like. These compounds may be used alone or in combination of two or more.
The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻² equivalent, preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻⁵ equivalent, more preferably 1 × with ^respect to 1 mol of the diol component. It is selected in the range of 10 ⁻⁷ to 1 × 10 ⁻³ equivalents.

  In addition, a catalyst deactivator can be added at a later stage of the reaction. As the catalyst deactivator to be used, a known catalyst deactivator is effectively used. Among them, sulfonic acid ammonium salt and phosphonium salt are preferable. Furthermore, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid and salts of paratoluenesulfonic acid such as tetrabutylammonium salt of paratoluenesulfonic acid are preferable.

  Further, as esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, Octyl paratoluenesulfonate, phenyl paratoluenesulfonate and the like are preferably used. Among these, dodecylbenzenesulfonic acid tetrabutylphosphonium salt is most preferably used.

  The amount of the catalyst deactivator used is preferably 0.5 to 50 mol per mol of the catalyst when at least one polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds is used. It can be used in a proportion, more preferably in a proportion of 0.5 to 10 mol, still more preferably in a proportion of 0.8 to 5 mol.

(Specific viscosity: η _SP )
The specific viscosity (η _SP ) of the polycarbonate resin of the present invention is in the range of 0.23 to 0.60, preferably in the range of 0.25 to 0.55, more preferably 0.30 to 0.50. More preferably, it is the range of 0.35-0.45. When the specific viscosity is less than 0.23, the strength of the injection-molded molded piece is lowered, and when it is more than 0.60, the molding processability at the time of injection molding is lowered, which is not preferable.
The specific viscosity referred to in the present invention was determined using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at 20 ° C.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]

  In addition, as a specific measurement of specific viscosity, it can carry out in the following way, for example. First, the polycarbonate resin is dissolved in 20 to 30 times the weight of methylene chloride, and the soluble component is collected by celite filtration, and then the solution is removed and dried sufficiently to obtain a solid component soluble in methylene chloride. Using a Ostwald viscometer, the specific viscosity at 20 ° C. is determined from a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride.

(Load deflection temperature)
The deflection temperature under load of the polycarbonate resin of the present invention is determined by ISO 178 using a test piece which was molded by injection molding machine J-75E3 manufactured by Japan Steel Works at a cylinder temperature of 240 ° C. after drying the polycarbonate resin pellets at 80 ° C. for 5 hours. It was measured in accordance. The load was measured at 1.80 MPa. For applications requiring electronic / electrical / OA equipment exterior parts and automotive interior / exterior parts, the deflection temperature under load is required to be at least 80 ° C., more preferably 90 ° C. or more.

<Colorant (C component)>
The black colored resin composition of the present invention contains 0.01 to 5 parts by weight of a colorant (component C) with respect to 100 parts by weight of the polycarbonate resin. The content of the colorant (component C) is preferably 0.1 to 4 parts by weight, and preferably 1 to 4 parts by weight. If it is less than 0.01 part by weight, jet black feeling cannot be obtained, and if it exceeds 5 parts by weight, the mechanical properties are deteriorated, which is not preferable. For the purpose of facilitating handling or improving dispersibility, the colorant may be granulated or added with a dispersant for the purpose of improving dispersibility.

  As the colorant (C component), carbon black (C-1 component) and / or black organic dye (C-2 component), which is a black inorganic pigment, can be used. The C-1 component and the C-2 component may be used in combination. Carbon black (component C-1), which is a black inorganic pigment, preferably contains 0.1 to 5 parts by weight, and 0.5 to 4 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin. It is more preferable that it contains 1 to 3 parts by weight. Within the above range, a jet black feeling is obtained, and it is difficult to cause a decrease in molecular weight or mechanical properties due to thermal decomposition during heating.

The black organic dye (component C-2) preferably contains 0.01 to 1 part by weight and preferably 0.03 to 0.5 part by weight with respect to 100 parts by weight of the aromatic polycarbonate resin. More preferably, it contains 0.05 to 0.3 parts by weight. Deep jetness can be obtained when it is in the above range.
The black organic dye is preferably composed of a combination of two or more dyes. Examples of the dye constituting the black organic dye include anthraquinone, perinone, perylene, azo, methine, and quinoline dyes. By using these dyes in combination, a black resin composition having particularly excellent jetness can be obtained. Specific examples of the dye include the following dyes.

  Examples of the anthraquinone dyes include Solvent Red 52, Solvent Red 111, Solvent Red 149, Solvent Red 150, Solvent Red 151, Solvent Red 168, Solvent Red 191, Solvent Red 207, Dispers Red 221, Dispers Red 22 , Solvent Blue 35, Solvent Blue 36, Solvent Blue 63, Solvent Blue 78, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Green 97, Solvent Green 97 Examples include dyes that are commercially available with color indexes such as een 20, Solvent Green 28, Disperse Violet 28, Solvent Violet 13, Solvent Violet 14, Solvent Violet 36, and the like.

  Examples of perinone-based dyes include dyes commercially available with color indexes such as Solvent Orange 60, Solvent Orange 78, Solvent Orange 90, Solvent Violet 29, Solvent Red 135, Solvent Red 162, and Solvent Red 179.

  Examples of perylene dyes include dyes commercially available with color indexes such as Solvent Green 3, Solvent Green 5, Solvent Orange 55, Vat Red 15, Vat Orange 7, F Orange 240, F Red 305, F Red 339, and F Yellow 83.

  Examples of the azo dye include Solvent Yellow 14, Solvent Yellow 16, Solvnt Yellow 21, Solvent Yellow 61, Solvent Yellow 81, Solvent Red 23, Solvent Red 24, Solvent Red 27, Solvent Red 84, Solvent Red 84, Solvent Red 84 Solvent Red 121, Solvent Red 132, Solvent Violet 21, Solvent Black 21, Solvent Black 23, Solvent Black 27, Solvent Black 28, Solvent Black 31, Solvent Orange 37, Solvent Orange 37 t Orange 40, a dye that is commercially available include the Color Index, such as Solvent Orange 45.

  Examples of methine dyes include dyes commercially available with color indexes such as Solvent Orange 80 and Solvent Yellow 93. Examples of quinoline dyes include Solvent Yellow 33 Solvent Yellow 98, Solvent Yellow 157, Disperse Yellow 54, Yellow 54, and Yellow. Dyes that are commercially available with a color index of

  Among the black organic dyes used in the present invention, anthraquinone dyes and methine dyes are preferably used. Among them, as the anthraquinone dyes, dark dyes such as purple, blue, and green, and methine are used. It is preferable to use a light-colored dye such as yellow as the system dye because a black resin composition having high depth and clarity and excellent jetness can be obtained.

<Light stabilizer (component D)>
The resin composition colored black in the present invention contains 0.01 to 5 parts by weight of a hindered amine light stabilizer (D component) with respect to 100 parts by weight of the polycarbonate resin. The content of the hindered amine light stabilizer (component D) is preferably 0.015 to 1 part by weight with respect to 100 parts by weight of the polycarbonate resin.
0.02-0.5 weight part is more preferable, and 0.03-0.1 weight part is further more preferable. If the content of the hindered amine light stabilizer (component D) is less than 0.01 parts by weight, the weather resistance is inferior, and if it exceeds 5 parts by weight, troubles such that volatile components adhere to the mold during molding are not preferable.

The hindered amine light stabilizer used in the present invention includes N—H type, N—CH ₃ type, and N—OR type, and N—CH ₃ type is particularly preferable. In the N—H type hindered amine light-resistant stabilizer, since it has high basicity, degradation such as hydrolysis may be promoted, and a significant decrease in molecular weight occurs in a humid heat environment. The N—CH ₃ type hindered amine light stabilizer having a structure in which a part of the piperidine structure is substituted with a methyl group is excellent in the balance between weather resistance and heat-and-moisture resistance, and has a low molecular weight and small hue change.

  Examples of the hindered amine light stabilizer used in the present invention include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate and bis (2,2,6,6-tetramethyl-1-octyloxy-4) didecanoate. -Piperidinyl) ester, bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-2-yl) amino] -6- (2-hydroxyethylamine) -1,3 , 5-triazine, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) ) Sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6) , 6-tetramethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetramethylpiperidine, bis (2 , 2,6,6-tetramethyl-4-piperidyl) diphenylmethane-p, p'-dicabamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3-disulfonate Hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) phenyl phosphite, nickel bis (octylphenyl sulfide, nickele Examples include complex of complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate, etc. These light stabilizers may be used alone or in combination of two or more. Good.

<Additives>
More preferably, the polycarbonate resin composition of the present invention can be blended with the following heat stabilizers, release agents and the like.

(Heat stabilizer)
The polycarbonate resin used in the present invention particularly preferably contains a heat stabilizer in order to suppress a decrease in molecular weight and a deterioration in hue during extrusion and molding. Examples of the heat stabilizer include a phosphorus heat stabilizer, a phenol heat stabilizer, and a sulfur heat stabilizer, and these can be used alone or in combination of two or more. Since the ether diol residue of the unit (A) is deteriorated by heat and oxygen and easily colored, it is preferable to contain a phosphorus heat stabilizer as the heat stabilizer. As the phosphorus stabilizer, a phosphite compound is preferably blended. Examples of the phosphite compound include pentaerythritol type phosphite compounds, phosphite compounds having a cyclic structure by reacting with dihydric phenols, and phosphite compounds having other structures.

  Specific examples of the pentaerythritol phosphite compound include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, And bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, and the like. Among them, distearyl pentaerythritol diphosphite and bis (2,4-di-ter - a butyl phenyl) pentaerythritol diphosphite.

  Examples of the phosphite compound having a cyclic structure by reacting with the above dihydric phenols include 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl). ) Phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-) tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) ) Phosphite, 2,2′-methylene-bis- (4,6-di-tert-butylphenyl) octyl phosphite, 6-tert-butyl Ru-4- [3-[(2,4,8,10) -tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] propyl] -2-methylphenol and the like.

  Examples of the phosphite compounds having other structures described above include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, and didecyl monophenyl phosphite. , Dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphos Phyto, Tris (diethylphenyl) phosphite, Tris (di-iso-propylphenyl) phosphite, Tris (di-n-butylphenyl) phosphite, Tris (2,4-di-te t- butylphenyl) phosphite, and tris (2,6-di -tert- butylphenyl) phosphite and the like.

In addition to various phosphite compounds, for example, phosphate compounds, phosphonite compounds, and phosphonate compounds can be mentioned.
Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-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-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
Among the above phosphorous heat stabilizers, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol Diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferably used.
Said phosphorus heat stabilizer can be used individually or in combination of 2 or more types. The phosphorus heat stabilizer is preferably blended in an amount of 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and still more preferably 0.01 to 0.3 part by weight per 100 parts by weight of the polycarbonate resin. The

The polycarbonate resin used in the present invention contains a hindered phenol-based heat stabilizer or sulfur-based heat stabilizer as a heat stabilizer for the purpose of suppressing molecular weight reduction and hue deterioration during extrusion and molding. It can also be added in combination with a system heat stabilizer.
The hindered phenol-based heat stabilizer is not particularly limited as long as it has an antioxidant function. For example, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t- Butylphenyl) propionate, tetrakis {methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate} methane, distearyl (4-hydroxy-3-methyl-5-tert-butylbenzyl) ) Malonate, triethylglycol-bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis {3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate}, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphene) L) propionate}, 2,2-thiodiethylenebis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, 2,2-thiobis (4-methyl-6-tert-butylphenol) 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxybenzyl) ) -Isocyanurate, 2,4-bis {(octylthio) methyl} -o-cresol, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,5,7,8 Tetramethyl-2 (4 ′, 8 ′, 12′-trimethyltridecyl) chroman-6-ol, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-t-butyl-a, a ', A "-(Messile -2,4,6-triyl) tri-p-cresol and the like.

Among these, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionate}, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-t-butyl-a, a ′, a ′-(mesitylene-2,4,6-triyl) Tri-p-cresol, 2,2-thiodiethylenebis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate} and the like are preferable.
These hindered phenol heat stabilizers may be used alone or in combination of two or more.
The hindered phenol heat stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and still more preferably 0.01 to 0.3 part by weight per 100 parts by weight of the polycarbonate resin. Blended.

  Examples of the sulfur heat stabilizer include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, diester Stearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), 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. . Among the above, pentaerythritol tetrakis (3-lauryl thiopropionate) is preferable.

One of these sulfur heat stabilizers may be used alone, or two or more thereof may be used in combination.
The sulfur-based heat stabilizer is preferably added in an amount of 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and still more preferably 0.01 to 0.3 part by weight per 100 parts by weight of the polycarbonate resin. The
When a phosphite heat stabilizer, a phenol heat stabilizer, and a sulfur heat stabilizer are used in combination, the total of these is preferably 0.001 to 1 part by weight, more preferably 0. 01 to 0.3 parts by weight is blended.

(Release agent)
The polycarbonate resin used in the present invention can be blended with a release agent within a range that does not impair the object of the present invention in order to further improve the releasability from the mold during melt molding.
Such release agents include higher fatty acid esters of mono- or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefin waxes, olefin waxes containing carboxy groups and / or carboxylic anhydride groups, silicone oils, Examples include organopolysiloxane.

The higher fatty acid ester is preferably a partial ester or a total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Such partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include, for example, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, stearyl stearate, behenic acid monoglyceride, behenic acid Behenyl, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphene -To, sorbitan monostearate, 2-ethylhexyl stearate and the like.
Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used.

As the higher fatty acid, a saturated fatty acid having 10 to 30 carbon atoms is preferable. Such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.
These release agents may be used alone or in combination of two or more. The amount of the release agent is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

<Other additives>
Besides, the polycarbonate resin composition of the present invention includes an ultraviolet absorber, a light stabilizer, an antistatic agent, a heat ray absorbent, a flame retardant, a hydrolysis improver, an inorganic filler, an antibacterial agent, a photocatalytic antifouling agent, A light diffusing agent, a white pigment for high light reflection, and the like can be contained. These can be contained by appropriately selecting agents and blending amounts that do not hinder the effects of the present invention.

<Black resin composition, black resin molded product>
In producing the black resin composition of the present invention, the production method is not particularly limited, and a known production method can be used. Usually, polycarbonate resin, additives, and colorants are premixed, then put into an extruder and melt-kneaded, and then the extruded thread is cooled and cut by a pelletizer to produce a pellet-shaped molding material . As the extruder, any of a single screw extruder and a twin screw extruder can be used, but a twin screw extruder is preferable from the viewpoint of productivity and kneadability. A typical example of such a twin screw extruder is ZSK (trade name, manufactured by Werner & Pfleiderer). Specific examples of similar types include TEX (trade name, manufactured by Nippon Steel Works, Ltd.), TEM (trade name, manufactured by Toshiba Machine Co., Ltd.), KTX (product name, manufactured by Kobe Steel, Ltd.), and the like. Can be mentioned. As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.

  Further, the additive and the colorant can be independently supplied to the extruder, but it is preferable to premix with the resin raw material as described above. Examples of such premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. A more suitable method is to prepare a master agent by mixing a part of the raw material and an additive with a high-speed stirrer such as a Henschel mixer, and then leave the total amount of the resin raw material and the high-speed component such as a Nauter mixer. It is a method of mixing with a stirrer not. The resin extruded from the extruder is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer and pelletized. When it is necessary to reduce the influence of external dust or the like, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods that have already been proposed are used to narrow the pellet shape distribution, further reduce miscuts, further reduce fine powder generated during transportation or transportation, and It is preferable to reduce bubbles (vacuum bubbles) generated in the strands and pellets. Miscuts can be reduced by controlling the thread temperature during cutting with a pelletizer, blowing ionic air during cutting, optimizing the rake angle of the pelletizer, and properly mixing the mold release agent, and cutting. And a method of filtering the mixture of the pellets and water to separate the pellets, water and miscuts. An example of the measuring method is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-200421. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. The black resin composition of the present invention can also obtain a desired molded product by a method such as injection molding, injection compression molding, injection blow molding, extrusion molding or blow molding.

The black resin composition of the present invention was measured in accordance with the paint general test method described in JIS K5600-5-4-Part 5: Mechanical properties of the coating film-Section 4: Scratch hardness (pencil method). The pencil hardness is F-2H. If the pencil hardness is less than F, the surface of the molded body is likely to be scratched, which is not preferable.
In the black resin composition of the present invention, the fracture mode of the low-temperature surface impact is ductile fracture, and the low-temperature impact property is excellent. The low temperature surface impact property was measured using a 2 mm thick square plate at a test temperature of −20 ° C., a test speed of 7 m / sec, a striker diameter of 1/2 inch and a receiving diameter of 1 inch using a high-speed impact tester. The probability of occasional brittle fracture is 50% or less. It is preferably 40% or less, more preferably 30% or less, particularly preferably 20% or less, and most preferably 15% or less. The maximum impact energy is 20 J or more. More preferably, it is 25J or more, More preferably, it is 30J or more, Most preferably, it is 35J or more. When the probability of the fracture form of the low-temperature surface impact being brittle fracture exceeds 50%, or when the maximum impact energy is less than 20 J, it may be difficult to use in a cold region.

(Blackness)
According to the JIS standard, on a glass surface with a refractive index of 1.567, the glossiness is 100% for an incident angle of 60 degrees, and the glossiness is 100 for a reflectance of 5% for an incident angle of 20 degrees.
The molded article formed from the black resin composition of the present invention has a glossiness of from 75 to 95, preferably from 80 to 95, preferably from 85 to 95, at an incident light receiving angle of 20 degrees measured according to JIS Z8741. Is more preferable. The glossiness at an incident light receiving angle of 60 degrees is from 80 to 100, preferably from 85 to 100, and more preferably from 90 to 100. If it is less than the above lower limit, the glossiness of the appearance is inferior, which is not preferable, and if it exceeds the above upper limit, the surface looks shining due to the reflected light, and thus it is not preferable because a gloss with a depth like a high-grade glass lacquer cannot be obtained. .

The molded article formed from the black resin composition of the present invention has a lightness (L *) measured in accordance with JIS Z8729 of 30 or less, more preferably 27 or less, and even more preferably 25 or less. Exceeding the upper limit is not preferable because the jetness of the appearance is inferior.
Glossiness at an incident light reception angle of 20 degrees is 75 to 95, glossiness at an incident light reception angle of 60 degrees is 80 to 100, and the color difference L * is 30 or less, which is excellent in jetness, like a high-grade glass lacquerware Appearance with a deep gloss.

  Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. In the examples, “parts” means “parts by weight”. The resins used and the evaluation methods used in the examples are as follows.

<Physical property evaluation>
1. Specific Viscosity A solution obtained by dissolving 0.7 g of polycarbonate resin pellets in 100 ml of methylene chloride was measured at 20 ° C. using an Ostwald viscometer (apparatus name: RIGO AUTO VISOSIMETER TYPE VMR-0525 · PC).
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]

2. Heat resistance evaluation (deflection temperature under load)
After the polycarbonate resin pellets were dried at 80 ° C. for 5 hours, a test piece that was injection-molded at a cylinder temperature of 240 ° C. and a mold temperature of 80 ° C. using an injection molding machine J-75E3 manufactured by Japan Steel Works, a load of 1. The deflection temperature under load was measured at 80 MPa. (Specimen shape: length 80 mm x width 10 mm x thickness 4 mm)

3. Pencil hardness Polycarbonate resin pellets are dried at 80 ° C. for 5 hours, and then molded with an injection molding machine J-75E3 manufactured by Nippon Steel Works at a cylinder temperature of 240 ° C. and a mold temperature of 80 ° C., and a black molded product (three-stage plate, thickness) 2 mm part). Using the molded test piece, measurement was performed by the base plate test method of JIS K5600.

4). High-speed surface impact test Using a black molded product obtained at the time of measuring the pencil hardness, a square plate having a thickness of 2 mm was tested using a high-speed impact tester Shimadzu HYDROSHOTHITS-P10 (Shimadzu Corporation) at a test temperature of -20 ° C. The test was conducted 10 times at a test speed of 7 m / sec, a striker diameter of 1/2 inch, and a receiving diameter of 1 inch, and the probability of brittle fracture (brittle fracture rate) and the maximum impact energy at that time were evaluated.

5. Weather resistance test Using a black molded product (three-stage plate, 2 mm thickness) obtained at the time of measuring the pencil hardness, and using Sunshine Weatherometer S80 manufactured by Suga Test Instruments Co., Ltd. according to JIS B7753, Sunshine carbon arc (ultra long life carbon 4 pairs) light source set to discharge voltage 50V, discharge current 60A, irradiation and surface spray (rainfall), black panel temperature 63 ° C, relative humidity 50% irradiation for 1000 hours Processed. The surface spray (rainfall) time was 12 minutes / 1 hour. A type glass filter was used. The specific viscosity (ηSP) at 20 ° C. of the solution obtained by dissolving 0.7 g of the molded piece in 100 ml of methylene chloride was measured with respect to the molded piece before and after the test, and the specific viscosity retention after the weather resistance test was measured. (Molecular weight retention) was determined. In the evaluation, the specific viscosity retention rate (molecular weight retention rate) was 95% or more, ◎, 90% or more and less than 95%, 、, 80% or more and less than 90%, or less than 80%.
ΔηSP = (ηSP1 / ηSP0) × 100
ΔηSP: specific viscosity retention ηSP1: specific viscosity after test ηSP0: specific viscosity before test

6). Wet heat test Using a black molded product (three-stage plate, 2 mm thickness) obtained at the time of measuring the pencil hardness and left at 85 ° C. and 85% RH for 1000 hours, 0.7 g of the molded piece Was dissolved in 100 ml of methylene chloride, the specific viscosity (ηSP) at 20 ° C. of the solution was measured, and the specific viscosity retention rate (molecular weight retention rate) after the wet heat test was determined. In the evaluation, the specific viscosity retention rate (molecular weight retention rate) was 95% or more, ◎, 90% or more and less than 95%, 、, 80% or more and less than 90%, or less than 80%.

7). Jetness Blackness was evaluated by glossiness evaluation and color difference evaluation.
(1) Glossiness evaluation Using a black molded product (three-stage plate, 3 mm thickness) obtained at the time of measuring the pencil hardness, in accordance with JIS Z8741, gloss meter (HORIBA IG-331, HORIBA) Were used, and the glossiness at an incident light receiving angle of 20 degrees and 60 degrees was measured.
(2) Lightness (L *)
Using a black molded product (three-stage plate, 3 mm thickness) obtained in the measurement of pencil hardness, and using an integrating sphere spectrophotometer CE-7000A (X-Rite) according to JIS Z8729 The lightness (L *) in the color difference formula CIE 1976 was measured using a D65 light source, a reflection method, a viewing angle of 10 degrees, and an SCI (including regular reflection light) method.

<Manufacture of polycarbonate resin>
[Example 1]
411 parts of isosorbide (hereinafter abbreviated as ISS), 66 parts of 1,9-nonanediol (hereinafter abbreviated as ND), 750 parts of diphenyl carbonate (hereinafter abbreviated as DPC), and tetramethylammonium hydroxide 0.8 × 10 ⁻ as a catalyst ² parts and 0.6 × 10 ⁻⁴ parts of sodium hydroxide were heated to 180 ° C. in a nitrogen atmosphere and melted. Thereafter, the degree of vacuum was adjusted to 13.4 kPa over 30 minutes. Thereafter, the temperature was raised to 250 ° C. at a rate of 60 ° C./hr, held at that temperature for 10 minutes, and then the degree of vacuum was set to 133 Pa or less over 1 hour. The reaction was carried out with stirring for a total of 6 hours. After completion of the reaction, the mixture was discharged from the bottom of the reaction tank under nitrogen pressure, and cooled with a water tank, and cut with a pelletizer to obtain a polycarbonate resin pellet having a specific viscosity of 0.401. .

For 100 parts by weight of the obtained pellets, 0.1 part by weight of C-2: NUBIAN BLACK PC-5857 (manufactured by Sumitomo Chemical; mixture of two or more dyes), which is a black organic dye, is used as a colorant. 0.05 parts by weight of D-1: Adekastab LA-52 (manufactured by ADEKA Co., Ltd.), which is an N—CH ₃ type hindered amine compound, is used as a stabilizer and E-1: Irgaphos 168 (manufactured by BASF) is 0 .05 parts by weight and hindered phenol stabilizer E-2: Irganox 1010 (manufactured by BASF) were mixed uniformly in 0.1 part by weight. Fabrication was performed. As the extruder, a vent type twin screw extruder (TEX30α-35BW-3V manufactured by Nippon Steel Works) having a diameter of 30 mmφ was used. Extrusion conditions were a discharge rate of 30 to 40 kg / h, a screw rotation speed of 250 rpm, a vacuum degree of vent of 3 kPa, and an extrusion temperature of 230 ° C. from the first supply port to the die part to obtain composition pellets. The evaluation results are shown in Table 1.

[Example 2]
The same operation as in Example 1 except that C-2: NUBIAN BLACK PC-5857 (manufactured by Sumitomo Chemical Co., Ltd .; mixture of two or more dyes) 0.25 parts by weight was used as the colorant. The same evaluation was performed. The results are shown in Table 1.

[Example 3]
The same evaluation as in Example 1 was performed, except that D-2: ADK STAB LA77Y (manufactured by ADEKA Corporation), which is an NH type hindered amine compound, was used as the light stabilizer. The results are shown in Table 1.

[Example 4]
The same evaluation as in Example 1 was performed except that 1.0 part by weight of C-1: carbon black (Mitsubishi Kasei Kogyo Co., Ltd. # 3600), which is a black pigment, was used as the colorant. . The results are shown in Table 1.

[Example 5]
The same evaluation as in Example 1 was performed except that 71 parts of 1,10-decanediol (hereinafter abbreviated as DD) was used instead of ND, and polycarbonate resin pellets having a specific viscosity of 0.394 were obtained. Went. The results are shown in Table 1.

[Example 6]
Except for using 451 parts of ISS, 69 parts of 1,12-dodecanediol (hereinafter abbreviated as DDD) and 750 parts of DPC as raw materials to obtain polycarbonate resin pellets having a specific viscosity of 0.398, the same operation as in Example 1 was performed. The same evaluation was performed. The results are shown in Table 1.

[Example 7]
The same evaluation as in Example 1 was performed except that polycarbonate resin pellets having a specific viscosity of 0.402 were obtained using 411 parts, ND99 parts, and 750 parts of DPC as raw materials. The results are shown in Table 1.

[Example 8]
The same operation as in Example 1 was carried out except that 0.1 part by weight of D-1: ADK STAB LA52 (manufactured by ADEKA), which is an N—CH ₃ type hindered amine compound, was used as the light stabilizer. Evaluation was performed. The results are shown in Table 1.

[Example 9]
The same evaluation as in Example 1 was performed except that 0.1 part by weight of D-2: ADK STAB LA77Y (manufactured by ADEKA), which is an NH type hindered amine compound, was used as the light stabilizer. Went. The results are shown in Table 1.

[Example 10]
The same operation as in Example 1 was performed except that 0.05 parts by weight of D-3: ADK STAB LA63P (manufactured by ADEKA), which is an N—CH ₃ type hindered amine compound, was used as the light stabilizer. Evaluation was performed. The results are shown in Table 1.

[Comparative Example 1]
The same evaluation as in Example 1 was performed except that polycarbonate resin pellets having a specific viscosity of 0.380 were obtained using ISS 391 parts, ND 121 parts, and DPC 750 parts as raw materials. The results are shown in Table 1.

[Comparative Example 2]
Except for obtaining polycarbonate resin pellets having a specific viscosity of 0.383 using 425 parts of ISS, 61 parts of 1,6-hexanediol (hereinafter abbreviated as HD) and 750 parts of DPC as raw materials, the same operation as in Example 1 was performed. The same evaluation was made. The results are shown in Table 1.

[Comparative Example 3]
Using 341 parts of ISS, 158 parts of 1,4-cyclohexanedimethanol (hereinafter abbreviated as CHDM) and 750 parts of DPC as raw materials, polycarbonate resin pellets having a specific viscosity of 0.382 were obtained. The same evaluation as in Example 1 was performed except that D-2: ADK STAB LA77Y (manufactured by ADEKA) was used as a light stabilizer with respect to 100 parts by weight of the obtained pellets. . The results are shown in Table 1.

[Comparative Example 4]
The same operation was performed except that 1.0 part by weight of C-1: carbon black (Mitsubishi Kasei Kogyo Co., Ltd. # 3600) was used as a colorant using bisphenol A type polycarbonate resin (Teijin Panlite L-1225Y), Similar evaluations were made. The results are shown in Table 1.

[Comparative Example 5]
The same operation was performed except that 0.3 parts by weight of C-2: NUBIAN BLACK PC-5857 (manufactured by Sumitomo Chemical) was used as a colorant using bisphenol A type polycarbonate resin (Teijin Panlite L-1225Y). The same evaluation was performed. The results are shown in Table 1.

[Reference Example 1]
Jetness evaluation was carried out using a commercially available high-quality glass lacquerware (100 mm square, thickness 3 mm, jet black tone, glossy). The evaluation results are shown in Table 1.

  Since the black resin composition and the black molded product of the present invention have excellent jet blackness and are excellent in low-temperature impact resistance, weather resistance, scratch resistance, and heat resistance, they are used in electronic / electric / OA equipment exterior parts, automobiles. Useful as interior / exterior parts, furniture, and musical instruments.

Claims (4)

The main repeating unit is the following formula

Unit (A) represented by the following formula

(In the formula, W represents an alkylene group having 8 to 12 carbon atoms.)
The molar ratio (A / B) of the unit (A) to the unit (B) is 80/20 to 95/5, and was measured with a 20 ° C. methylene chloride solution. With respect to 100 parts by weight of a copolymer polycarbonate resin having a specific viscosity of 0.23 to 0.60 and a deflection temperature under load of 80 ° C. or more, 0.01 to 5 parts by weight of a colorant (component C), and a hindered amine light stability A black resin composition comprising 0.01 to 5 parts by weight of an agent (D component), wherein the resin composition satisfies the following characteristics (1) to (4):
(1) The pencil hardness measured in accordance with JIS K5600-5-4 is F to 2H. (2) The maximum impact energy of a high-speed surface impact test according to ASTM D3763 is 20 J or more in an environment of -20 ° C. The brittle fracture rate is 50% or less. (3) The glossiness at an incident light reception angle of 20 degrees measured in accordance with JIS Z8741 is 75 or more and 95 or less, and the glossiness at an incident light reception angle of 60 degrees is 80 or more. (4) The lightness (L *) measured in accordance with JIS Z8729 of a molded product (thickness 3 mm) molded from the resin composition is 30 or less.   The black resin composition according to claim 1, wherein the colorant (component C) is an organic dye and contains 0.01 to 1 part by weight with respect to 100 parts by weight of the polycarbonate resin. 2. The black resin composition according to claim 1, wherein the light stabilizer (component D) is an N—CH ₃ type hindered amine light stabilizer and contains 0.01 to 1 part by weight with respect to 100 parts by weight of the polycarbonate resin. .   The black molded product formed by shape | molding the black resin composition of any one of Claims 1-3.