JP2009249563A - Rotation-molded molding having light diffusabiity - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rotation-molded molding made of a polycarbonate resin exhibiting excellent light duffusability by an air bubble. <P>SOLUTION: This rotation-molded molding having light duffusability is formed by rotation-molding a polycarbonate granule, wherein the polycarbonate granule contains a particle having a size larger than 60 mesh obtained by a standard sieve method according to a Tyler sieve at 50-100 wt.% of ratio, and a major diameter of the particle having the size larger than 60 mesh is more than 2.5 times and 10.0 times or less of a minor diameter that is a width of the particle orthogonal to the major diameter. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a rotational molded body having good light diffusibility by bubbles formed by rotational molding of a polycarbonate resin powder. More specifically, the present invention relates to a rotational molded body having good light diffusibility due to air bubbles formed by rotational molding of a polycarbonate resin particle having a specific shape.

  Conventionally, rotational molding is known as a method for obtaining a large-sized resin molded product with relatively inexpensive equipment. Conventionally, however, the main object has been limited to olefin resins and the like. In recent years, the rotational molding method has been progressing rapidly.

  Conventionally, it was a method of passing through a high-temperature furnace for a long time while rotating the mold. At present, a technique for passing a heat medium and a refrigerant directly through a mold and a technique for efficiently passing the medium through the mold have been developed, and a more complicated or precise molded product can be obtained than before.

  With the progress of rotational molding, the target resin is diversified, and the demand for manufacturing engineering plastics such as polycarbonate resin by rotational molding in place of conventional general-purpose resins is increasing. In particular, aromatic polycarbonate has a high demand for a large-sized rotational molded body from the viewpoints of transparency, impact characteristics, electrical characteristics, flame retardancy, and dimensional stability.

  A rotary molded body made of a polycarbonate resin often requires light diffusibility in which an internal light source cannot be directly seen and the entire rotary molded body emits light. In general, when imparting light diffusibility to a polycarbonate resin, a method of adding a diffusing agent having a refractive index different from that of a polycarbonate resin such as an acrylic resin or a silicon resin as in Patent Document 1 is used.

However, the method of adding a diffusing agent to the polycarbonate resin is costly, and further, there is a problem that discoloration occurs during rotation molding by adding the diffusing agent. In addition, a method of injecting a supercritical inert gas into a molten polycarbonate resin for foaming is known for injection molding or the like, but the general method cannot be used for rotational molding in which no pressure is applied to the molten resin.
JP 2008-19405 A

  An object of the present invention is to provide a rotational molded body that exhibits good light diffusibility by bubbles formed by rotational molding of a polycarbonate resin granular material.

  The present inventor has thoroughly considered the change in the resin state in the rotational molding in order to solve the above-mentioned problems, and as a result of intensive studies, the specific particle of the polycarbonate resin granular material is good by defining its shape. The inventors have found that bubbles that exhibit light diffusibility can be generated, and have reached the present invention.

That is, according to the present invention,
1. A rotationally molded product obtained by rotationally molding a polycarbonate resin particle, wherein the polycarbonate resin particle has a ratio of particles larger than 60 mesh obtained by a standard sieving method using a Tyler sieve at 50 to 100% by weight. Rotating molding having light diffusibility, characterized in that the major axis of the particles larger than 60 mesh is more than 2.5 times the minor axis which is the width of the particles perpendicular to the major axis and 10.0 times or less body,
2. The rotary molded article according to item 1 above, wherein the average particle diameter of the polycarbonate resin granules is in the range of 0.1 to 6 mm, and the average diameter of the major axis of the particles larger than 3.60 mesh is in the range of 0.65 to 20 mm. The rotationally molded article according to the preceding item 1,
Is provided.

  The polycarbonate resin used in the present invention will be described below. The production method of the polycarbonate resin is not particularly limited, but it is usually obtained by reacting a dihydric phenol and a carbonate precursor by an interfacial polycondensation method or a melt transesterification method. Or obtained by polymerizing by a ring-opening polymerization method of a cyclic carbonate compound.

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl). Phenyl} methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A) ), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4 -Hydroxy-3,5-dibromo) phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane 2,2-bis {(4-hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2, 2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2- Bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4 -Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bi {(4-hydroxy-3-methyl) phenyl} fluorene, α, α′-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, 4,4 ′ -Dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester, etc. The above can be mixed and used.

  Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3 -Methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) A homopolymer or copolymer obtained from at least one bisphenol selected from the group consisting of 3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene Preferably, furthermore, a homopolymer of bisphenol A and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl Copolymers of rucyclohexane and bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane or α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used. Is done. In particular, a homopolymer of bisphenol A is preferred.

  As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing polycarbonate resin by reacting the above dihydric phenol and carbonate precursor by interfacial polycondensation method or melt transesterification method, oxidation of catalyst, terminal terminator and dihydric phenol is prevented as necessary. An antioxidant or the like may be used. The polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or may be a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid, Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

  Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2,4,6-trimethyl-2. , 4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1- Tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [1,1-bis (4- Hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-di Hydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among others, 1,1, 1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable. preferable.

When a polyfunctional compound that produces such a branched polycarbonate resin is included, the ratio is 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, particularly preferably 0.01 to 0, based on the total amount of polycarbonate. .3 mol%. In particular, in the case of the melt transesterification method, a branched structure may be generated as a side reaction. The amount of the branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0.5 mol in the total amount of the polycarbonate. %, Particularly preferably 0.01 to 0.3 mol%. Such a ratio can be calculated by ¹ H-NMR measurement.

  The reaction by the interfacial polycondensation method is usually a reaction between a dihydric phenol and phosgene, and is reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide or tetra-n-butylphosphonium bromide, a quaternary ammonium compound or a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

  In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such end terminators. Monofunctional phenols are commonly used as end terminators for molecular weight control, and the resulting polycarbonate resins are compared to those that do not because the ends are blocked by groups based on monofunctional phenols. Excellent thermal stability. Such monofunctional phenols are generally phenols or lower alkyl-substituted phenols, and can be monofunctional phenols represented by the following general formula (1).

（式中、Ａは水素原子または炭素数１〜９の直鎖または分岐のアルキル基あるいはフェニル基置換アルキル基であり、ｒは１〜５、好ましくは１〜３の整数である。）

(In the formula, A is a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3.)

  Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

  In addition, as other monofunctional phenols, phenols or benzoic acid chlorides having a long chain alkyl group or an aliphatic polyester group as a substituent, or long chain alkyl carboxylic acid chlorides can also be shown. Among these, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.

（式中、Ｘは−Ｒ−Ｏ−、−Ｒ−ＣＯ−Ｏ−または−Ｒ−Ｏ−ＣＯ−である、ここでＲは単結合または炭素数１〜１０、好ましくは１〜５の二価の脂肪族炭化水素基を示し、ｎは１０〜５０の整数を示す。）

Wherein X is —R—O—, —R—CO—O— or —R—O—CO—, wherein R is a single bond or a carbon number of 1 to 10, preferably 1 to 5; A valent aliphatic hydrocarbon group, and n represents an integer of 10 to 50.)

  As the substituted phenols of the general formula (2), those having n of 10 to 30, particularly 10 to 26 are preferable, and specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, Examples include eicosylphenol, docosylphenol, and triacontylphenol.

  Further, as the substituted phenols of the general formula (3), those in which X is —R—CO—O— and R is a single bond are suitable, and those in which n is 10 to 30, particularly 10 to 26. Specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

  It is desirable that the end terminator is introduced at the end of at least 5 mol%, preferably at least 10 mol%, based on the total end of the obtained polycarbonate resin. More preferably, the terminal terminator is introduced in an amount of 80 mol% or more with respect to all terminals, that is, the terminal hydroxyl group (OH group) derived from the dihydric phenol is more preferably 20 mol% or less, particularly preferably. This is the case where 90 mol% or more of the terminator is introduced with respect to all terminals, that is, the OH group is 10 mol% or less. Moreover, you may use a terminal terminator individually or in mixture of 2 or more types.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the alcohol or phenol produced by mixing the dihydric phenol and the carbonate ester with heating in the presence of an inert gas. Is carried out by distilling the water. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system is evacuated to about 1.33 × 10 ^{3 to} 13.3 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

  Examples of the carbonate ester include esters such as an optionally substituted aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among them, diphenyl carbonate is preferable.

A polymerization catalyst can be used to increase the polymerization rate. Examples of such polymerization catalyst include sodium hydroxide, potassium hydroxide, sodium salt of dihydric phenol, alkali metal compounds such as potassium salt, calcium hydroxide, Alkaline earth metal compounds such as barium hydroxide and magnesium hydroxide, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine, alkoxides of alkali metals and alkaline earth metals, alkali metals Organic salts of alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds manganese compounds , Titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. A catalyst may be used independently and may be used in combination of 2 or more type. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻³ equivalent, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalent, relative to 1 mol of dihydric phenol as a raw material. Selected by range.

  In the polymerization reaction, in order to reduce phenolic end groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate, bis ( It is preferable to add compounds such as (phenylphenyl) carbonate, chlorophenylphenyl carbonate, bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate and ethoxycarbonylphenylphenyl carbonate. Of these, 2-chlorophenyl phenyl carbonate, 2-methoxycarbonylphenyl phenyl carbonate and 2-ethoxycarbonylphenyl phenyl carbonate are preferable, and 2-methoxycarbonylphenyl phenyl carbonate is particularly preferably used.

  Furthermore, it is preferable to use a deactivator that neutralizes the activity of the catalyst in such a polymerization reaction. Specific examples of the deactivator include, for example, benzene sulfonic acid, p-toluene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, p-toluene sulfone. Sulfonic acid esters such as methyl acid, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate; trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene , Methyl acrylate-sulfonated styrene copolymer, dodecylbenzenesulfonate-2-phenyl-2-propyl, dodecylbenzenesulfonate-2-phenyl-2-butyl, octylsulfonate tetrabutylphospho Salts, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tetrahexylphosphonium dodecylbenzenesulfonate, tetradecylbenzenesulfonate tetra Octyl phosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl dimethyl ammonium methyl sulfate, tetramethyl ammonium hexyl sulfate Over DOO, decyl trimethyl ammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds can be used in combination.

  Among the quenching agents, those of phosphonium salt or ammonium salt type are preferred. The amount of the catalyst is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst, and 0.01 to 500 ppm, more preferably 0 with respect to the polycarbonate resin after polymerization. 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

  The polycarbonate resin granule of the present invention is a granule composed of a polycarbonate resin composition, and preferably has a viscosity average molecular weight of 13,000 to 50,000. The viscosity average molecular weight is preferably 15,000 to 30,000, more preferably 16,000 to 23,000.

  Such a viscosity average molecular weight is a factor having a great influence on the melt viscosity of the resin at the time of rotational molding. At the time of rotational molding, the following two points are satisfied: (i) the resin is uniformly melted from the mold wall surface, and (ii) the resin powder is melted while flowing on the molten liquid surface. A uniform and defect-free wall thickness is formed. However, when the melt viscosity of the resin is high, the resistance when flowing on the melt surface becomes high, and it becomes difficult to form a uniform melt layer. On the other hand, by carrying out fine control of the mold temperature, a good rotational molded body may be obtained even when the melt viscosity is high.

  When the viscosity average molecular weight is less than 13,000, the strength of the product tends to be insufficient, and when it exceeds 50,000, it is difficult to obtain a good molded product. A method for controlling the viscosity average molecular weight of the polycarbonate resin and the polycarbonate resin composition has been widely known so far, and can be appropriately set depending on the purpose.

  Also, two or more polycarbonate resins having different viscosity average molecular weights may be mixed. In this case, it is naturally possible to mix a polycarbonate resin having a viscosity average molecular weight outside the above range. For example, a polycarbonate resin having a viscosity average molecular weight of 80,000 or more, more preferably a polycarbonate resin having a viscosity average molecular weight of 100,000 or more is mixed, and a molecular weight distribution of two peaks is obtained by a method such as GPC (gel permeation chromatography). It can also be used.

The viscosity average molecular weight in the present invention means that the polycarbonate resin composition is dissolved in 20 to 30 times its weight of methylene chloride, and the soluble component is collected by celite filtration, and then the solution is removed and dried sufficiently. Thus, a methylene chloride-soluble solid is obtained. From a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride, the specific viscosity at 20 ° C. calculated by the following formula is obtained using an Ostwald viscometer.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀ [t ₀ is the falling seconds of methylene chloride, t is the falling seconds of the sample solution]

Further, the viscosity average molecular weight M is obtained by inserting the specific viscosity obtained above by the following formula.
η _SP /c=[η]+0.45×[η] ² c
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  In the polycarbonate resin granular material used in the present invention, the proportion of particles larger than 60 mesh obtained by the standard sieving method using a Tyler sieve is 50 to 100% by weight, and preferably 55 to 100% by weight. Particles passing through a 60 mesh obtained by a standard sieving method using a Tyler sieve of such a granular material are unlikely to generate bubbles during rotational molding. Therefore, the proportion of particles passing through 60 mesh is 50% by weight or less, preferably 45% by weight or less.

  Further, in the polycarbonate resin granular material used in the present invention, the major axis (longest part) of particles larger than 60 mesh exceeds 2.5 times the minor axis, which is the width of particles perpendicular to the major axis, and 10 0.0 or less. It is preferable that the major axis exceeds 3.0 times the minor axis. Further, the major axis is preferably 8.0 times or less of the minor axis, and more preferably 5.0 times or less. When the major axis of the longest part of the particle is 2.5 times the minor axis, which is the width of the particle perpendicular to the major axis, the gas in the atmosphere is trapped when the powder is melted by rotational molding. And no bubbles are generated.

  The average particle diameter of the polycarbonate resin particles used in the present invention is not particularly limited, but is preferably 0.1 to 6 mm, more preferably 0.3 to 3.5 mm, and particularly preferably 0.5 to 3.0 mm. Moreover, the average diameter of the major axis of the particles larger than 60 mesh is preferably in the range of 0.65 to 20 mm, more preferably in the range of 0.8 to 10 mm, and in the range of 0.9 to 5 mm. Is more preferable. If the particle size of the powder is too large, it takes time to melt at the time of rotational molding, and another problem such as high temperature retention occurs.

  As a method for obtaining a polycarbonate resin granular material satisfying such conditions, (1) a method of classifying the polycarbonate resin granular material, and (2) a die diameter and a take-off speed when the polycarbonate resin granular material is extruded by an extruder. For example, a method of adjusting the thread diameter and the cut length with a pelletizer can be used. Also, (3) a method of pulverizing polycarbonate resin pellets of various sizes or various molded products, (4) a method of treating polycarbonate resin granules with various mechanochemical devices, and (5) in a solution of polycarbonate resin Can be used according to the purpose as appropriate.

  The polycarbonate resin composition constituting the polycarbonate resin granular material of the present invention can contain various thermoplastic resins and additives depending on the purpose.

  Examples of thermoplastic resins other than polycarbonate resin include polyethylene resin, polypropylene resin, polystyrene resin, polyacryl styrene resin, ABS resin, AS resin, AES resin, ASA resin, SMA resin, polyalkyl methacrylate resin, etc. General-purpose plastics, polyphenylene ether resin, polyacetal resin, aromatic polyester resin, polyamide resin, cyclic polyolefin resin, engineering plastics represented by polyarylate resin (amorphous polyarylate, liquid crystalline polyarylate), poly So-called super engineering plastics such as ether ether ketone, polyether imide, polysulfone, polyether sulfone, polyphenylene sulfide, etc. It can be mentioned. Furthermore, thermoplastic elastomers such as styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers can also be used.

  Other various additives include, for example, reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fiber, glass bead, glass balloon, milled fiber, glass flake, carbon fiber, carbon flake, carbon bead, carbon milled Fiber, metal flake, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica, ceramic particle, ceramic fiber, aramid particle, aramid fiber, polyarylate fiber, graphite, conductive carbon black, various whiskers Flame retardant (halogen, phosphate ester, metal salt, red phosphorus, silicon, metal hydrate, etc., including anti-dripping agent), heat stabilizer, UV absorber, light stability Agent, mold release agent, lubricant, colorant (carbon black, acid Pigments and dyes such as titanium), light diffusing agents (acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, calcium carbonate particles, etc.), fluorescent brighteners, phosphorescent pigments, fluorescent dyes, antistatic agents, flow modifiers , Crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), impact modifiers typified by graft rubber, infrared absorbers, and photochromic agents. it can. In particular, the light diffusing agent can be used for the purpose of enhancing the light diffusing effect by the bubbles of the present invention. Even when a light diffusing agent is added, the addition amount can be reduced in the present invention, and problems such as discoloration can be solved.

  It is preferable that the polycarbonate resin composition which comprises the polycarbonate resin granular material of this invention contains a phosphorus stabilizer as a heat stabilizer. As the phosphorus stabilizer, any of phosphite, phosphonite, and phosphate can be used.

［式中Ｒ^１は、水素または炭素数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^１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。］ Various phosphite stabilizers can be used in the present invention. Specifically, for example, it is a phosphite compound represented by the general formula (4).

[Wherein R ¹ represents hydrogen 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 (the alkyl group is C 1-30) or a hydroxy substituent, and three R ^{1 s} 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^２、Ｒ^３はそれぞれ水素、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。尚、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。］ Moreover, the phosphite compound represented by General formula (5) can be mentioned.

Wherein R ² and R ³ are each hydrogen, 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 a cyclohexane having 4 to 20 carbon atoms. An alkyl group and a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms are 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^４、Ｒ^５は炭素数１２〜１５のアルキル基である。尚、Ｒ^４およびＲ^５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。］ Moreover, the phosphite compound represented by General formula (6) can be mentioned.

[Wherein R ⁴ and R ⁵ are each an alkyl group having 12 to 15 carbon atoms. Note that R ⁴ and R ⁵ can be selected either in the same manner or different from each other. ]

［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。］ Examples of the phosphonite stabilizer include phosphonite compounds represented by the following general formula (7) and phosphonite compounds represented by the following general formula (8).

[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. ]

  Preferred examples of the phosphite compound corresponding to the general formula (4) include diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenyl mono ( Tridecyl) phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite.

  Preferred examples of the phosphite compound corresponding to the general formula (5) 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, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. That. Such phosphite compounds can be used alone or in combination of two or more.

  Preferable specific examples of the phosphite compound corresponding to the general formula (6) include 4,4'-isopropylidenediphenol tetratridecyl phosphite.

  Preferred specific examples of the phosphonite compound corresponding to the general formula (7) 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-propylphenyl) ) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n-butylphenyl) -4,4'- Phenylenediphosphonite, 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 corresponding to the general formula (8) 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-butylphenyl) Nyl) -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- Although it is possible to use one or two of phenyl-phenylphosphonite (E3-1 component) and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite in combination, A mixture of the two types is preferred. 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 a phosphate stabilizer, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, Dioctyl phosphate, diisopropyl phosphate and the like can be mentioned, and trimethyl phosphate is preferred.

  As a more preferable phosphorus stabilizer with respect to said phosphorus stabilizer, the compound shown by the following general formula (9) and (10) can be mentioned.

（式（９）中、Ｒ^６およびＲ^７は、それぞれ炭素原子数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 (9), R ⁶ and R ⁷ each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.)

（式（１０）中、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１４、Ｒ^１５、およびＲ^１６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^１２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^１３は水素原子またはメチル基を示す。）

(In Formula (10), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or An aralkyl group, R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹³ represents a hydrogen atom or a methyl group.)

In the formula (9), R ⁶ and R ⁷ are preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. Specific examples of the compound of the formula (9) include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) Phosphite, Tris (2,4-di-tert-butylphenyl) phosphite, Tris (2,6-di-tert-butylphenyl) phosphite, Tris (2,6-di-tert-butylphenyl) phosphite In particular, tris (2,4-di-tert-butylphenyl) phosphite is preferable.

  On the other hand, the phosphorus compound of the formula (10) can be produced by a known method. For example, there is a method of reacting a bisphenol compound represented by the following general formula (11) with phosphorus trichloride to obtain the corresponding phosphoric chloride, and then reacting it with a phenol represented by the following general formula (12). .

（式（１１）中、Ｒ^８、Ｒ^９、Ｒ^１０、およびＲ^１１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^１２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^１３は水素原子またはメチル基を示す。）

(In the formula (11), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ 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 ¹² represents hydrogen. And represents an atom or an alkyl group having 1 to 4 carbon atoms, and R ¹³ represents a hydrogen atom or a methyl group.)

（式（１２）中、Ｒ^１４、Ｒ^１５、およびＲ^１６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 (12), R ¹⁴ , R ¹⁵ and R ¹⁶ 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 (11) 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, which can be preferably used.

  More preferably, the compound of the general formula (11) is 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).

  On the other hand, specific examples of the compound of the general formula (12) 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. Can be preferably used. More preferred as a specific example of the compound of the general formula (12) is a case having two or more alkyl substituents.

  The polycarbonate composition constituting the polycarbonate resin granular material of the present invention preferably contains a phenolic antioxidant. 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- ', 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-hydroxy) Phenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3- Droxy-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 can be 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.

  The polycarbonate resin composition constituting the polycarbonate resin granular material of the present invention preferably contains a sulfur-based antioxidant. Specific examples of such sulfur-based antioxidants include dilauryl-3,3′-thiodipropionic acid ester, ditridecyl-3,3′-thiodipropionic acid ester, dimyristyl-3,3′-thiodipropionic acid ester. , 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-based stabilizer, phenol-based antioxidant, and sulfur-based antioxidant listed above can be used alone or in combination of two or more. More preferably, it is a case where a phosphorus stabilizer is used in combination, and it is particularly preferable that the phosphorus stabilizer contains the compound of the above general formula (9) or general formula (10). More preferred is a case where three components of a phosphorus stabilizer, a phenolic antioxidant, and a sulfurous antioxidant are used as essential components. Even in such a case, it is preferable that the compound of the above general formula (9) or general formula (10) is contained as a phosphorus stabilizer.

  The proportion of these stabilizers in the composition is 0.0001 to 1 part by weight of the phosphorus stabilizer, phenol antioxidant, or sulfur antioxidant, respectively, with respect to 100 parts by weight of the polycarbonate resin. It is preferable. More preferably, it is 0.0005-0.5 weight part with respect to 100 weight part of polycarbonate resin. More preferably, it is 0.001-0.2 weight part.

  The polycarbonate resin composition constituting the polycarbonate resin particle of the present invention preferably contains a release agent. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound (silicone oil) Silicone resins, etc., which may be modified with functional group-containing compounds such as acid modification), fluorine compounds (fluorine oils typified by polyfluoroalkyl ethers), paraffin wax, beeswax and the like. .

  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 release agent is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

  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.

  Also, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2n-butyl malonate, 1,2,3,4-butanecarboxylic acid and 2,2, Condensate of 6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanedicarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol Condensates with tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethy -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] Undecane) Diethano 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 Condensation with ', β'-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol, polymethylpropyl 3-oxy- [4- (2, A hindered amine-based light stabilizer represented by 2,6,6-tetramethyl) piperidinyl] siloxane can also be blended.

  The ratio 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 with respect to 100 parts by weight of the polycarbonate resin.

  In addition, a blueing agent can be blended in the polycarbonate resin composition of the present invention in order to counteract the yellowish color based on an ultraviolet absorber or the like. Any bluing agent can be used without any problem as long as it is 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 name “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 AG, generic name: Solvent Blue 97 [trade name: “Macrolex Blue RR” manufactured by Bayer AG], and generic name: Solvent Blue 45 [CA. No. 61110; trade name “Terrazol Blue RLS” manufactured by Sand Corp.], Ciba Specialty Chemicals' Macrolex Violet, Terrazol Blue RLS, etc., particularly Macrolex Blue RR, Macrolex Violet B and Terrazol Blue RLS is preferred. These bluing agents are usually blended in the polycarbonate resin at a concentration of 0.3 to 1.2 ppm.

  Arbitrary methods are employ | adopted in order to manufacture the polycarbonate resin composition of this invention. For example, polycarbonate resin and optionally other components are mixed thoroughly using premixing means such as V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc., and in some cases, extrusion granulator and briquetting machine For example, granulation may be performed by using a melt kneader represented by a vent type biaxial ruder, and pelletizing with a device such as a pelletizer.

  In addition, a method in which the polycarbonate resin and optionally other components are independently supplied to a melt kneader represented by a vented biaxial rudder, the polycarbonate resin and optionally a part of other components are premixed, and the remaining The method of supplying to a melt-kneader independently of these components 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.

  The rotational molding machine used when rotationally molding the polycarbonate resin granular material of the present invention is not particularly limited. However, it is preferable to be able to directly heat and cool the rotational molding die because there is no temperature unevenness inside the die and excellent molding efficiency. An example of such a rotary molding machine is “GYRO SPACE” system manufactured by Gangnam Special Industrial Co., Ltd. More preferably, a device equipped with a facility for reducing the pressure inside the mold is preferable.

  Rotational molding can obtain a particularly large molded product with low distortion. Therefore, it is suitable for obtaining various glazing materials, lighting covers, large containers, etc. as such a rotational molded body, and is suitably used in a wide range of fields such as aircraft, ships, vehicles, electronic / electrical equipment, mechanical devices, etc. It is.

  The polycarbonate resin rotational molded body obtained by the present invention is suitable for obtaining various glazing materials, lighting covers, large containers, and the like, because it exhibits good light diffusibility due to air bubbles. Is exceptional.

  The following examples further illustrate the present invention. In addition, this invention is not limited to this Example. Evaluation was based on the following method.

  (1) Appearance of molded product: Five rotational molded articles were molded, and the appearance was visually observed to confirm whether light diffusibility was expressed by bubbles.

(2) Shape and distribution of polycarbonate resin particles: A polycarbonate resin particle having a size larger than 60 mesh was taken by a standard sieving method using a Tyler sieve, and a mass ratio was measured to obtain a weight ratio of 60 mesh on. Further, 60 mesh on was observed at 50 times with a videoence microscope made by Keyence. In the measurement, the longest part of the two-dimensionally observed particles was taken as the major axis, and the maximum value of the particle width perpendicular to the major axis was taken as the minor axis. Measurements were made on 500 powder particles, the ratio of the major axis to the minor axis was calculated, and the average value was obtained. Furthermore, the average value of the major axis was obtained.
The average particle size of the polycarbonate resin particles was measured by laser diffraction particle size distribution measurement.

(3) Measurement of viscosity average molecular weight: The viscosity average molecular weight (M) of the polycarbonate resin was measured using a Ostwald viscometer using a specific viscosity (η _sp) determined from a solution of 0.7 g of the polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C. ) Was inserted into 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

[Examples 1-3, Comparative Examples 1-3]
The raw materials shown in Table 1 were added to a V-type blender in the amounts shown in the table and then mixed to obtain a uniform mixture. The mixture was extruded at a cylinder temperature of 270 ° C. while vent suction was performed at a vacuum degree of 3000 Pa with a biaxial ruder having a diameter of 30 mm [manufactured by Nippon Seisakusho TEX-30] to obtain pellets. The obtained pellets were pulverized by the following pulverization method (Method A or Method B).

The obtained polycarbonate resin composition granules were dried at 120 ° C. for 5 hours using a hot air dryer, and then subjected to rotational molding using “GYRO SPACE” manufactured by Gangnam Special Industries Co., Ltd. After setting the mold set temperature to about 300 ° C. through 300 ° C. oil, 1 kg of the granular material was put into the mold. At this temperature, rotation was performed under the conditions of a rotation speed of the main shaft of 50 rpm and a rotation speed of the small shaft rotating with the main shaft of 50 rpm, and the rotation was performed for about 15 minutes. After that, oil at room temperature is added, and the mold temperature is gradually cooled to near room temperature, and further rotation is continued for about 18 minutes. After the rotation is stopped, the container molding shown in FIGS. 1 and 2 is performed from inside the mold. The product was taken out and evaluated as described above.
In addition, the symbol which shows each polycarbonate resin composition of Table 1, and the grinding | pulverization method are as follows.

PC1: Polycarbonate resin with a viscosity average molecular weight of 18,100 produced by the phosgene method PC2: Polycarbonate resin with a viscosity average molecular weight of 23,500 produced by the phosgene method B1: Tris (2,4-di-tert-butylphenol) phosphite (Irgafos 168 manufactured by Ciba Japan)
B2: Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076 manufactured by Ciba Japan Co., Ltd.)
B3: Tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite (Clariant Japan Sandstub P-EPQ) was conditioned at 50 ° C. and 95% RH for 24 hours, Used by crushing.
B4: Pentaerythritol tetrakis (3-lauryl thiopropionate) (Sumitomo Chemical's Sumitizer TP-D)
B5: Pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (Irganox 1010 manufactured by Ciba Japan)
UV1: 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole (Chemisorb 79 manufactured by Chemipro Kasei Co., Ltd.)
L1: Glycerol monostearate (Rikenmar S-100A manufactured by Riken Vitamin Co., Ltd.)
L2: Alkyl monostearate and alkyltriglycerin mixture (RIKENMAL SL-900A manufactured by Riken Vitamin Co., Ltd.)
L3: Pentaerythritol tetrastearate (Roxyol VPG861 manufactured by Cognis)
CL1: Anthraquinone dye (Bayer Macrolex Violet B)
CL2: Anthraquinone dye (Bayer Macrolex Blue RR)
N1: potassium perfluorobutyl sulfonate (Megafac F-114 manufactured by Dainippon Ink & Chemicals, Inc.)
N2: Diphenylsulfone-3-sulfonic acid potassium salt (KSS manufactured by Seal Sand Chemicals)
N3: Phosphorus flame retardant (FG-1500, manufactured by Kinkai Chemical Co., Ltd.)
Pulverization method-A method: The polycarbonate resin pellets were pulverized by a pulverizer at room temperature, and the pulverized product was subjected to sieve classification.
Pulverization method-B method: The polycarbonate resin pellets were pulverized by a pulverizer at room temperature, and the pulverized product was subjected to sieve classification. Thereafter, the pulverized product was introduced into a stirrer and stirred in an atmosphere of 140 ° C.

It is a front view of a container molded product. It is a bottom side side view of a container mold product.

Explanation of symbols

1 Container-shaped molded product body (spherical shape, thickness approx. 2 mm)
2 Front center line of container mold product (vertical direction)
3 Molded product diameter (360mm)
4 Bottom missing sphere (perforated) part 5 Bottom missing sphere (perforated) part diameter (140 mm)

Claims (3)

  A rotationally molded product obtained by rotationally molding a polycarbonate resin particle, wherein the polycarbonate resin particle has a ratio of particles larger than 60 mesh obtained by a standard sieving method using a Tyler sieve at 50 to 100% by weight. Rotating molding with light diffusivity, characterized in that the major axis of the particles larger than 60 mesh is more than 2.5 times the minor axis which is the width of the particles perpendicular to the major axis and 10.0 times or less body.   The rotational molded body according to claim 1, wherein the average particle diameter of the polycarbonate resin granular material is in the range of 0.1 to 6 mm.   The rotational molded body according to claim 1, wherein the average diameter of the major axis of particles larger than 60 mesh is in the range of 0.65 to 20 mm.

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