JP2002020496A - Polycarbonate resin granule, and rotational molding product composed thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce polycarbonate resin granules suited in rotational molding. SOLUTION: The polycarbonate resin granules are composed of a polycarbonate resin composition which has (1) a viscosity average molecular weight of 13,000-23,000 and (2) not greater than 3 wt.% particles having a particle diameter of greater than 35 mesh obtained in the standard sieve method by the Tyler mesh and not greater than 5 wt.% particles having a particles diameter of smaller than 150 mesh, and rotational molding products are obtained by subjecting such resin granules to rotational molding.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polycarbonate resin particle. More specifically, the present invention provides a polycarbonate resin composition having a specific form, which is particularly suitable for rotational molding.

[0002]

2. Description of the Related Art Polycarbonate resins are used in a wide variety of fields because of their excellent properties such as transparency and impact resistance. For example, they are used for optical information media, optical lenses, and glazing materials for buildings and vehicles. Can be mentioned. These are mainly used as various molded articles by extrusion molding, injection molding, heat compression molding and the like.

[0003] On the other hand, as a method for obtaining a large-sized resin molded product by relatively inexpensive equipment, rotary molding has been conventionally known. However, conventionally, its main object has been limited to olefin-based resins and the like. In recent years, the method of rotational molding has been rapidly developing. Conventionally, a method has been used in which a mold is rotated and passed through a high-temperature furnace for a long time. At present, a technique for directly passing a heat medium and a coolant through a mold and a technique for efficiently passing the medium into the mold have been developed, and a more complicated or precise molded product than ever before can be obtained.

[0004] With the progress of the rotational molding, the target resins have been diversified, and there has been an increasing demand for manufacturing engineering plastics such as polycarbonate resins by rotational molding in place of conventional general-purpose resins.

However, unlike extrusion molding and injection molding, rotational molding has a drawback that bubbles are easily generated in the resin because it is substantially difficult to apply a high pressure to the resin. In particular, it is extremely difficult to satisfy such a requirement with a polycarbonate resin having a high melt viscosity, and due to generation of air bubbles, an appearance or an optical requirement of a molded product is insufficient, or an element having an unstable mechanical strength. There was a problem with

"8.6 Rotational molding method" in polycarbonate resin handbook (Seiichi Homma, published by Nikkan Kogyo Shimbun)
In the above section, examples of rotational molding conditions are shown, but such conditions were not sufficient to obtain a rotational molded body of stable quality.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin powder suitable for rotational molding. The present inventor has studied the changes in the resin state during rotational molding in order to solve the above problems, and as a result of intensive studies, the polycarbonate resin has a specific molecular weight, and as a granular material satisfying the specific conditions. The present inventors have found that a problem can be solved by performing rotational molding, and have reached the present invention.

[0008]

SUMMARY OF THE INVENTION The present invention provides a powdery and granular material comprising a polycarbonate resin composition, which (1) has a viscosity average molecular weight of 13,000 to 23,000,
(2) The present invention relates to a polycarbonate resin particle having a particle size larger than 35 mesh obtained by a standard sieving method using a Tyler sieve and having a particle size of 35% or less and 3% or less and a particle size smaller than 150 mesh of 5% by weight or less. .

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

Representative examples of the dihydric phenol used herein include hydroquinone, resorcinol, 4,4
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 known 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-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α, α′-bis (4- Hydroxyphenyl) -o-
Diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α
α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy Diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy diphenyl ketone, 4,4'-dihydroxy diphenyl ether, 4,4'-dihydroxy diphenyl ester and the like, and these may be used alone or in combination of two or more. 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
A homopolymer obtained from at least one bisphenol selected from the group consisting of -hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, or Copolymers are preferred, and furthermore, bisphenol A homopolymer and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis {(4-hydroxy- Copolymers with 3-methyl) phenyl} propane or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used. In particular, a homopolymer of bisphenol A is preferred.

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

In producing the polycarbonate resin by reacting the above-mentioned dihydric phenol with the carbonate precursor by the interfacial polycondensation method or the melt transesterification method, if necessary, a catalyst, a terminal stopper and an oxidation of the dihydric phenol may be carried out. May be used. Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, Further, a mixture of two or more of the obtained polycarbonate resins may be used.

Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 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} -trisphenol such as α, α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ) Ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof.
1-tris (4-hydroxyphenyl) ethane, 1,
1,1-Tris (3,5-dimethyl-4-hydroxyphenyl) ethane is preferred, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferred.

When the composition contains a polyfunctional compound capable of producing such a branched polycarbonate resin, the proportion is preferably 0.001 to 1 mol%, preferably 0.1 to 0.1 mol%, based on the total amount of the polycarbonate.
005 to 0.5 mol%, particularly preferably 0.01 to 0.
3 mol%. In particular, in the case of the melt transesterification method,
In some cases, a branched structure may occur as a side reaction.
It is preferably from 01 to 1 mol%, preferably from 0.005 to 0.5 mol%, particularly preferably from 0.01 to 0.3 mol%. The ratio can be calculated by ¹ H-NMR measurement.

The reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and is carried out 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. Also,
To promote the reaction, for example, triethylamine, tetra-n
Catalysts such as tertiary amines such as -butylammonium bromide and tetra-n-butylphosphonium bromide, quaternary ammonium compounds and quaternary phosphonium compounds can also be used. At that time, the reaction temperature is usually 0 to
40 ° C., reaction time is about 10 minutes to 5 hours, 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 a terminal stopper. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, and the resulting polycarbonate resins are capped by groups based on monofunctional phenols, so that Excellent heat stability. Such a monofunctional phenol is generally a phenol or a lower alkyl-substituted phenol, and may be a monofunctional phenol represented by the following general formula (1).

[0018]

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Wherein A is a hydrogen atom or a group having 1 to 9 carbon atoms.
Is a linear or branched alkyl group or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3. Specific examples of the above monofunctional phenols include, for example, phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

Further, other monofunctional phenols include:
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic polyester group as a substituent, or long-chain alkylcarboxylic acid chlorides can also be used. Among these, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.

[0021]

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[0022]

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(Wherein X is -RO-, -R-CO-O
— Or —RO—CO—, wherein R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms, and n represents an integer of 10 to 50. Show. )

The substituted phenols of the general formula (2) are preferably those having n of 10 to 30, especially 10 to 26, and specific examples thereof include, for example, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, Octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol and the like can be mentioned.

Further, as the substituted phenols of the general formula (3), a compound in which X is -R-CO-O- and R is a single bond is suitable, and n is 10 to 30, especially 10 to 26.
Are preferred, and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Examples include tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

It is desirable that the terminal terminator is introduced at least at 5 mol%, preferably at least 10 mol%, based on all terminals 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 dihydric phenol is more preferably 20 mol% or less, and particularly preferably. This is the case when 90 mol% or more of the terminal terminator is introduced to all the terminals, that is, when the OH group is 10 mol% or less. Further, the terminal stoppers may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and is produced by mixing the dihydric phenol and the carbonate ester while heating in the presence of an inert gas. It is performed by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but is usually 120 to 350 ° C.
Range. In the late stage of the reaction, the system was set at 1.33 × 10 ³ -1.
The distillation of alcohol or phenol generated by reducing the pressure to about 3.3 Pa is facilitated. Reaction time is usually 1-4
About an hour.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms. Specifically, diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like can be mentioned, with diphenyl carbonate being preferred.

Further, in order to increase the polymerization rate, a polymerization catalyst is used.
The polymerization catalyst can be used, for example, water
Sodium oxide, potassium hydroxide, dihydric phenol
Alkali metal compounds such as thorium and potassium salts, water
Calcium oxide, barium hydroxide, magnesium hydroxide
Alkaline earth metal compounds such as tetramethylammonium
Hydroxide, tetraethylammonium hydroxide
Nitrogen containing sid, trimethylamine, triethylamine, etc.
Basic compounds, alkali metals and alkaline earth metals
Lucoxides, organic alkali metals and alkaline earth metals
Acid salts, zinc compounds, boron compounds, aluminum
Compounds, silicon compounds, germanium compounds, organic
Tin compounds, lead compounds, osmium compounds, ann
Timon compounds, manganese compounds, titanium compounds, di
Normal esterification reactions such as ruconium compounds,
The catalyst used in the exchange reaction can be used. Touch
The medium may be used alone or in combination of two or more.
May be used. The amount of these polymerization catalysts used is
Preferably 1 × 10 ^-8~
1 × 10^-3Equivalent, more preferably 1 × 10^-7~ 5 × 10
^-FourIt is selected within the range of equivalents.

In the polymerization reaction, in order to reduce the number of phenolic terminal groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
It is preferable to add compounds such as bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate, and ethoxycarbonylphenylphenyl carbonate. Above all, 2-
Chlorophenyl phenyl carbonate, 2-methoxycarbonyl phenyl phenyl carbonate and 2-ethoxycarbonyl phenyl phenyl carbonate are preferred, and 2-methoxy carbonyl phenyl phenyl carbonate is particularly preferred.

Further, it is preferable to use a deactivator for neutralizing the activity of the catalyst in such a polymerization reaction. Specific examples of this deactivator include, for example, benzenesulfonic acid, p-toluenesulfonic acid, methylbenzenebenzenesulfonic acid, ethylbenzenebenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, phenylbenzenebenzenesulfonic acid, p-toluenesulfonic acid. Sulfonates such as methyl acrylate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate; further, trifluoromethanesulfonic acid, naphthalenesulfonic acid, and sulfonated polystyrene , Methyl acrylate-sulfonated styrene copolymer, 2-phenyl-2-propyl dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid-2-
Phenyl-2-butyl, octylsulfonic acid tetrabutylphosphonium salt, decylsulfonic acid tetrabutylphosphonium salt, benzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetraethylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfone Acid tetrahexyl phosphonium salt, dodecyl benzene sulfonic acid tetraoctyl 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 Chill sulfate, tetramethylammonium hexyl sulfate, decyltrimethylammonium 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 deactivators, those of the phosphonium salt or ammonium salt type are preferred. The amount of such a catalyst is preferably 0.5 to 50 mol per 1 mol of the remaining catalyst, and 0.01 to 500 ppm, more preferably 0 to 500 ppm, based on the polycarbonate resin after polymerization. It is used at a rate of 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

The polycarbonate resin powder of the present invention comprises:
A powder comprising a polycarbonate resin composition,
(1) The viscosity average molecular weight is from 13,000 to 23,000.
0 (hereinafter, may be referred to as “condition 1”). Preferably, the viscosity average molecular weight is 1
5,000 to 20,000, more preferably 1
6,000 to 19,500.

The viscosity average molecular weight is a factor that has a great influence on the melt viscosity of the resin during rotational molding. At the time of rotational molding, by satisfying the following two points, (i) the resin is uniformly melted from the mold wall surface, and (ii) the resin particles are melted while flowing on the melt surface. A uniform, defect-free wall thickness is formed. However, when the melt viscosity of the resin is high, the resistance when flowing on the surface of the melt becomes high, and it becomes difficult to form a uniform molten layer.

If the viscosity average molecular weight is less than 13,000, the strength of the product tends to be insufficient, and if it exceeds 23,000, it becomes difficult to obtain a good molded product. Methods for controlling the viscosity average molecular weight of the polycarbonate resin and the polycarbonate resin composition have been widely known, and can be appropriately set according to the purpose.

Also, two or more kinds of polycarbonate resins having different viscosity average molecular weights may be mixed. In this case, it is of course possible to mix with 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 the two peak molecular weight distribution is determined by a method such as GPC (gel permeation chromatography). What has it can also be used.

In the present invention, the viscosity average molecular weight is
The polycarbonate resin composition is dissolved in 20 to 30 times the weight of methylene chloride, and the solubles are collected by filtration through celite. The solution is removed and dried sufficiently to obtain a solid of methylene chloride solubles. . From a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride, a specific viscosity at 20 ° C. calculated by the following equation is determined using an Ostwald viscometer. Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀ [t ₀ is the number of seconds of falling methylene chloride, t is the number of seconds of falling of the sample solution]

Further, the viscosity average molecular weight M was determined by inserting the specific viscosity determined above into the following equation. η _SP /c=[η]+0.45×[η] ² c [η] = 1.23 × 10 ^-4 M ^0.83 c = 0.7

The polycarbonate resin particles of the present invention include:
(2) Satisfies that 3% by weight or less of particles larger than 35 mesh and 5% by weight or less of particles smaller than 150 mesh obtained by the standard sieving method using a Tyler sieve (hereinafter, referred to as below). Such a condition is referred to as “condition 2”
). More preferably, particles larger than 35 mesh are 2% by weight or less, and particles smaller than 150 mesh are 4% by weight or less. More preferably, particles larger than 35 mesh are 1% by weight or less, and particles smaller than 150 mesh are 4% by weight or less.

The particle size distribution of the powder has a great influence on the uniformity of melting during rotational molding. When a component having a large particle size in the powder and granule is melted and restrained by the surface of the molten liquid, such a portion hinders the movement of another powder and granule. Therefore, formation of a uniform molten layer is hindered. On the other hand, a powder having a small particle diameter has a large surface area with respect to volume, and thus is easily softened by heat. Such a powder acts as a medium to bind other powders, resulting in a large particle. A granular material is formed. For this reason, it is preferable that the powdery particles satisfy the above condition 2.

The method of obtaining the polycarbonate resin composition particles satisfying the above condition 2 includes: 1) a method of classifying the polycarbonate resin composition powder particles, and 2) a method of extruding the polycarbonate resin composition by an extruder. And a method of adjusting the thread diameter and the cut length thereof with a pelletizer according to the die diameter and the take-up speed. On the other hand, as a method for obtaining the polycarbonate resin particles, in addition to the above 2), (i) a method of pulverizing a polycarbonate resin composition pellet having a normal size or various molded articles, and (ii) a method of pulverizing the polycarbonate resin particles. Examples of the method include a method of treating powder and granules such as other additives with various mechanochemical devices, and a method of (iii) mixing various additives in a solution of a polycarbonate resin and removing a solvent from the solution. Can be appropriately used according to the purpose.

Further, in the present invention, for the same reason as described above, particles larger than 35 mesh obtained by a standard sieve method using a Tyler sieve after the test described below account for 3% by weight or less, preferably 2% by weight or less. Some are more preferable (these conditions may be hereinafter referred to as “condition 3”).

That is, even when the above condition 1 is satisfied, a difference may be seen in the finished product and the yield of the rotomolded body. Examination of such causes revealed that not only the particle size of the granular material but also its shape was a factor that affected rotational molding. That is, it can be said that the condition 3 is a screening method for discriminating a granular material from which a better rotary molded body can be obtained.

The influence of the shape of the powder is considered as follows. The polycarbonate resin composition has extremely high toughness as compared with other general-purpose resins. Therefore, when a pellet or a compact is pulverized and classified to obtain a powder, the destruction occurs in a ductile manner. Therefore, on the surface of the granular material, a small-diameter portion (a so-called mustache) in which a part of the granular material is elongated tends to be provided. Such a whisker portion has a large surface area and is easily melted, and is easily combined with other powders. As a result, the state is the same as the presence of a powder having a large particle diameter. Therefore, even when the overall particle size satisfies the condition 2, it is considered that there is a difference in rotational moldability.

Here, the test method under the condition 3 is 500 ml
Put about 100 g of polycarbonate resin particles in a round flask, and place the flask in an oil bath or the like controlled at a temperature specified below so that the whole particles are below the oil bath liquid level, After the temperature is stabilized, the powder in the flask is stirred for 30 minutes at a rotation speed of about 60 rpm, and then the particle size distribution is measured using a standard sieve. The set temperature here is
According to JIS K7207, the temperature shall be 5 ° C. lower than the deflection temperature under load measured under a load of 1.82 MPa.

As a method for obtaining the polycarbonate resin particles satisfying the above condition 3, the rake angle and the twist angle of the cutter blade of the pelletizer, Alternatively, by adjusting the cutting temperature or the like, it may be mentioned that a beard-like substance is not generated in the obtained granular material. In such a case, an ideal powder can be obtained by obtaining the powder by a so-called hot cut method. In addition, when pulverization is performed to obtain a powdery or granular material, by adjusting the pulverizing blade and rotation speed of the pulverizer, the pulverization temperature, and the like, a whisker-like substance is not similarly generated.

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

The thermoplastic resin other than the polycarbonate resin includes, for example, polyethylene resin, polypropylene resin, polystyrene resin, polyacrylstyrene resin, ABS resin, AS resin, AES resin, ASA resin,
General-purpose plastics represented by SMA resin, polyalkyl methacrylate resin, etc., polyphenylene ether resin, polyacetal resin, aromatic polyester resin,
Engineering plastics represented by polyamide resin, cyclic polyolefin resin, polyarylate resin (amorphous polyarylate, liquid crystal polyarylate), etc.
So-called super engineering plastics such as polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, and polyphenylenesulfide can be mentioned. Further, thermoplastic elastomers such as styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, polyester-based thermoplastic elastomer, and polyurethane-based thermoplastic elastomer can also be used.

As other various additives, for example, reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fiber, glass beads, glass balloon,
Milled fiber, glass flake, carbon fiber, carbon flake, carbon beads, carbon milled fiber,
Metal flake, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica,
Ceramic particles, ceramic fibers, aramid particles, aramid fibers, polyarylate fibers, graphite, conductive carbon black, various whiskers, etc., flame retardants (halogen, phosphate ester, metal salt, red phosphorus, silicon, metal) Hydrate, etc., including anti-dripping agents), heat stabilizers, UV absorbers, light stabilizers, release agents, lubricants, coloring agents (pigments and dyes such as carbon black and titanium oxide), light diffusion Agents (cross-linked acrylic particles, cross-linked silicon particles, ultra-thin 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 represented by graft rubber, infrared absorbers, and photochromic agents Can be blended.

The polycarbonate resin composition constituting the polycarbonate resin particles of the present invention preferably contains a phosphorus-based stabilizer as a heat stabilizer. As the phosphorus-based stabilizer, any of phosphite-based, phosphonite-based, and phosphate-based stabilizers can be used.

Various phosphite stabilizers can be used in the present invention. Specifically, for example, general formula (4)

[0052]

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[Wherein R ¹ is hydrogen or C 1-20
An alkyl group, an aryl group or alkaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a halo or alkylthio (the alkyl group has 1 to 3 carbon atoms)
0) or a hydroxy substituent, and the three R ^{1 s} can be selected either identically or differently,
Further, a cyclic structure can be selected by being derived from a dihydric phenol. ] It is a phosphite compound represented by these.

In addition, the general formula (5)

[0055]

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[Wherein R ² and R ³ each represent hydrogen and carbon number 1
An alkyl group having 20 to 20 carbon atoms, an aryl group or an alkylaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms,
And represents 25 2- (4-oxyphenyl) propyl-substituted aryl groups. The cycloalkyl group and the aryl group can be selected from those not substituted with an alkyl group and those substituted with an alkyl group. And a phosphite compound represented by the following formula:

The general formula (6)

[0058]

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Wherein R ⁴ and R ⁵ are an alkyl group having 12 to 15 carbon atoms. Note that R ⁴ and R ⁵ may be the same or different from each other. And a phosphite compound represented by the following formula:

Examples of the phosphonite stabilizer include a phosphonite compound represented by the following general formula (7) and a phosphonite compound represented by the following general formula (8).

[0061]

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[0062]

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[Wherein, Ar ¹ and Ar ^{2 each} represent an aryl group or an alkylaryl group having 6 to 20 carbon atoms, or
It represents 5 to 25 2- (4-oxyphenyl) propyl-substituted aryl groups, and the four Ar ^{1 s} can be the same or different. Alternatively, ^two Ar ² may be the same or different. ]

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

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

Preferred 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 above 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'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butyl) Phenyl)-
4,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3 ′
-Biphenylenediphosphonite; tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite is preferred; tetrakis (2,4-di-t
(tert-butylphenyl) -biphenylenediphosphonite is more preferred. This tetrakis (2,4-di-te
(rt-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)
One kind of -4,3'-biphenylenediphosphonite (E2-2 component) and tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite (E2-3 component) Alternatively, two or more of them can be used in combination, but a mixture of these three is preferred. In the case of three kinds of mixtures, the mixing ratio is E2-1.
Component, E2-2 component and E2-3 component in a weight ratio of 10
The range of 0:37 to 64: 4 to 14 is preferable, and 100:
The range of 40-60: 5-11 is more preferable.

Preferred specific examples of the phosphonite compound corresponding to the above 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-te
rt-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)-
3-phenyl-phenylphosphonite and the like, and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferable, and bis (2,4-di-te
(rt-butylphenyl) -phenyl-phenylphosphonite is more preferred. This screw (2,4-di-tert)
-Butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more, specifically, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite (E3-1 component). )and,
Bis (2,4-di-tert-butylphenyl) -3-
One or two of phenyl-phenylphosphonite can be used in combination, but a mixture of these two is preferred. In the case of two types of mixtures, the mixing ratio is
The weight ratio is preferably in the range of 5: 1 to 4, more preferably 5: 2 to 3.

On the other hand, examples of the phosphate stabilizers include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl phosphate, tribubutoxyethyl phosphate, and the like. Examples thereof include dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate, and preferred is trimethyl phosphate.

More preferable phosphorus stabilizers for the above phosphorus stabilizers include the following general formulas (9) and (1)
0).

[0071]

Embedded image

(In the formula (9), R ⁶ and R ⁷ each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group,
It represents an aryl group or an aralkyl group. )

[0073]

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(In the formula (10), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ ,
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, and 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. Equation (9)
Specific examples of the compound of (1) include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, and tris ( 2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-t
tert-butylphenyl) phosphite and the like, and particularly preferred is tris (2,4-di-tert-butylphenyl) phosphite.

On the other hand, the phosphorus compound of the formula (10) can be produced by a known method. For example, a bisphenol compound represented by the following general formula (11) is reacted with phosphorus trichloride to obtain a corresponding phosphoric acid chloride, and thereafter, it is reacted with the following general formula (1)
There is a method of reacting with phenol shown in 2).

[0077]

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(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; 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.)

[0079]

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(In the formula (12), R ¹⁴ , R ¹⁵ and R ¹⁶
Represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, respectively. )

Specific examples of the compound represented by the general formula (11) include 2,2′-methylenebisphenol and 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-ter
t-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) and 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol) and the like, and they can be preferably used.

More preferably, the compound of the general formula (11) is 2,2'-methylenebis (4-methyl-6-te
rt-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, −te
rt-butyl-4-methylphenol, 2,4-di-t
tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-
Methylphenol, 2,4-dimethyl-6-tert-
Butylphenol, 2,6-di-tert-butyl-4
-Ethylphenol, 2,4,6-tri-tert-butylphenol, and 2,6-di-tert-butyl-4-s-butylphenol, and the like can be preferably used. A more preferred 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 particles of the present invention preferably contains a phenolic antioxidant. Various phenolic antioxidants can be used.

Specific examples of such a phenolic antioxidant include, for example, vitamin E, n-octadecyl-β-
(4'-hydroxy-3 ', 5'-di-tert-butylfell) 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-ter
t-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'-methylenebis (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-t
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-te
rt-butyl-5-methyl-2-hydroxybenzyl)
Phenyl] 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-ter
t-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-ter
t-butylphenol), 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di-te
rt-butylanilino) -1,3,5-triazine,
N, N'-hexamethylenebis- (3,5-di-ter
t-butyl-4-hydroxyhydrocinnamide), N,
N'-bis [3- (3,5-di-tert-butyl-4
-Hydroxyphenyl) propionyl] hydrazine,
1,1,3-tris (2-methyl-4-hydroxy-5
-Tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert)
-Butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris (3,5-di-ter
t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-
Hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-ter
t-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like, It can be used preferably.

More preferably, n-octadecyl-β-
(4'-hydroxy-3 ', 5'-di-tert-butylfell) 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-te
rt-butyl-4-hydroxyphenyl) propionate] methane, and furthermore n-octadecyl-β- (4 ′
-Hydroxy-3 ', 5'-di-tert-butylfell) propionate is preferred.

The polycarbonate resin composition constituting the polycarbonate resin particles of the present invention preferably contains a sulfur-based antioxidant. Specific examples of such sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate. , Distearyl-3,3'-
Thiodipropionate, lauryl stearyl-
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. More preferably, pentaerythritol tetra (β-laurylthiopropionate) ester can be mentioned.

The above-mentioned phosphorus stabilizers, phenolic antioxidants and sulfur antioxidants can be used alone or in combination of two or more. More preferably, a phosphorus-based stabilizer is used as an essential component. Particularly, as the phosphorus-based stabilizer, the above-mentioned general formula (9) or (1)
It preferably contains the compound of 0). More preferred is a case where three components of a phosphorus-based stabilizer, a phenolic antioxidant, and a sulfur-based antioxidant are used in combination as essential components. Even in such a case, it is preferable that the compound of the general formula (9) or the general formula (10) is contained as a phosphorus-based stabilizer.

The proportion of these stabilizers in the composition is as follows: 100% by weight of the polycarbonate resin composition contains 0.0001 to 1% by weight of a phosphorus-based stabilizer, a phenolic antioxidant, or a sulfur-based antioxidant. %. More preferably, it is 0.0005 to 0.5% by weight in 100% by weight of the polycarbonate resin composition.
More preferably, the content is 0.001 to 0.2% by weight.

The polycarbonate resin composition constituting the polycarbonate resin particles 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 .; those modified with a functional group-containing compound such as acid modification can also be used), silicone compound (silicone oil) , A silicone resin, etc. Those modified with a functional group-containing compound such as acid modification can also be used), a fluorine compound (fluorine oil represented by polyfluoroalkyl ether, etc.), paraffin wax, beeswax and the like. .

Preferred release agents include saturated fatty acid esters, for example, monoglycerides such as stearic acid monoglyceride, polyglycerin fatty acid esters such as decaglycerin decastearate and decaglycerin tetrastearate, and stearic acid stearates. Lower fatty acid esters, higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used. The release agent is 0.01% in 100% by weight of the resin composition.
It is preferably about 2% by weight.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 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) methane and the like.

As the ultraviolet absorber, for example, 2-
(2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert)
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'
-Di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-ter
t-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" -tetraphthalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl ) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-te)
rt-butylphenyl) -5-chlorobenzotriazole, 2,2 ′ methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], methyl -3- [3-ter
Benzotriazole ultraviolet absorbers represented by condensates with t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol can be mentioned.

Further, as an ultraviolet absorber, for example, 2-
(4,6-diphenyl-1,3,5-triazine-2-
Yl) -5-hexyloxy-phenol, 2- (4,
6-bis- (2,4-dimethylphenyl-1,3,5-
Examples thereof include hydroxyphenyltriazine compounds such as triazin-2-yl) -5-hexyloxy-phenol.

Further, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2n-butylmalonate,
Condensate of 2,3,4-butanecarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanedicarboxylic acid with 1,2,2 Condensation product of 6,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)-
1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2 , 2,6,6-tetramethylpiperidyl) imino]}, poly {[6-morpholino-s-triazine-2,4-diyl] [(2,2,6
6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetra Methyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,
Condensation product with 4,8,10-tetraoxaspiro [5,5] undecane) diethanol, N, N′-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-
Butyl-N- (1,2,2,6,6-pentamethyl-4
-Piperidyl) amino] -chloro-1,3,5-triazine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β , Β, β ', β'-tetramethyl-3,9
-(2,4,8,10-tetraoxaspiro [5,5]
A condensate with undecane) diethanol and a hindered amine-based light stabilizer represented by polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane can also be blended.

The ratio of the ultraviolet absorber and the light stabilizer is as follows:
It is 0.01 to 5% by weight, more preferably 0.02 to 1% by weight, in 100% by weight of the resin composition.

Further, a bluing agent can be added to the polycarbonate resin composition of the present invention in order to cancel a yellowish color due to an ultraviolet absorber or the like. As the bluing agent, any one can be used without any particular difficulty as long as it is used for a polycarbonate resin. Generally, anthraquinone dyes are easily available and preferred. As a specific bluing agent, for example, a common name Solv
ent 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 Vi
olet31 [CA. No. 68210; brand name "Diaresin Violet D" manufactured by Mitsubishi Chemical Corporation], generic name Solvent Violet 33 [CA. No.607
25; brand name "Diaresin Blue J" manufactured by Mitsubishi Chemical Corporation], and 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; brand name “Macrolex Violet 3R” manufactured by Bayer AG], generic name Sol
vent Blue 97 [trade name “Macrolex Blue RR” manufactured by Bayer AG] and generic name Solvent
Blue 45 [CA. No. 61110; Trade name "Terazole Blue RLS" manufactured by Sando Co., Ltd.], Macrovax Violet and Terrazol Blue RLS manufactured by Ciba Specialty Chemicals, and the like. RLS is preferred.

For producing the polycarbonate resin composition of the present invention, any method is employed. For example, after sufficiently mixing the polycarbonate resin and optionally other components using a pre-mixing means such as a V-blender, a Henschel mixer, a mechanochemical device, an extruder, and the like, an extrusion granulator or a briquetting machine is optionally used. Granulation, and then melt-kneading with a melt-kneading machine represented by a vent-type twin-screw rudder, and pelletizing with a device such as a pelletizer.

In addition, a method of independently supplying a polycarbonate resin and optionally other components to a melt kneader typified by a vented twin-screw ruder, premixing a part of the polycarbonate resin and optionally other components Thereafter, a method in which the remaining components are independently supplied to a melt kneader, or the like, may also be used. If there is a liquid component,
A so-called liquid injection device or liquid addition device can be used for supply to the melt kneader.

The polycarbonate resin composition of the present invention can obtain a desired molded product by various methods.
As a molding method, various methods known as a usual method for molding a thermoplastic resin composition can be used, and examples thereof include extrusion molding, injection molding, and compression molding. However, as described above, the polycarbonate resin composition of the present invention is particularly suitable for rotational molding.

The rotational molding machine used for rotationally molding the polycarbonate resin particles of the present invention is not particularly limited. However, the one that can directly heat and cool the rotary mold directly, without the temperature unevenness inside the mold,
It is preferable because of excellent molding efficiency. As such a rotary molding machine, for example, "GYRO SPA" manufactured by Gangnam Special Sangyo Co., Ltd.
CE "system and the like.

Rotational molding makes it possible to obtain particularly large molded products with low distortion. Therefore, such a rotomolded body is suitable for obtaining various glazing materials, lighting covers, large containers, and the like.
It is suitably used in a wide range of fields such as electric equipment and mechanical devices.

[0103]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples. Note that the present invention is not limited to the embodiment. The evaluation was based on the following method. (1) Appearance of molded article Five pieces of the rotomolded article were molded, the appearance was visually observed, and the number of molded articles having defects such as generation of bubbles was obtained. (2) Screening test for condition 3 Whether about 100 g of polycarbonate resin particles were placed in a 500 ml round flask, the flask was immersed in an oil bath at 130 ° C. as shown in FIG. After confirming that the temperature of the granular material reached 130 ° C. (about 15 minutes was required), the granular material in the flask was further cooled to 60 ° C. for 30 minutes.
After stirring at rpm, the obtained granules were subjected to standard particle size distribution using a Tyler sieve to determine the particle size distribution. (3) Measurement of viscosity average molecular weight The viscosity average molecular weight of the obtained polycarbonate resin powder was measured based on the method described in the text.

[Examples 1 to 4 and Comparative Example 1] The raw materials shown in Table 1 were charged into a V-type blender in the amounts shown in the table, and then mixed to obtain a uniform mixture. The mixture is 30 mm in diameter.
The mixture was extruded at a cylinder temperature of 270 ° C. while venting and suctioning at a vacuum of 3000 Pa using a biaxial ruder [Kobe Steel Works KTX-30]. The obtained pellets were pulverized by the following pulverization method (method A or B) and classified using a sieve to obtain a powder.

The obtained polycarbonate resin composition powder was dried at 120 ° C. for 5 hours using a hot air drier, and then subjected to rotational molding using “GYRO SPACE” manufactured by Gangnam Special Sangyo Co., Ltd. After setting the mold set temperature to about 330 ° C. through the oil of 330 ° C., the powder 1 is placed in the mold.
kg. At such a temperature, the rotation speed of the main shaft is 50 rpm
m, the small shaft rotating together with the main shaft was rotated at a rotation speed of 50 rpm, and rotated for about 15 minutes. After that, rotation was continued for about 18 minutes while adding the oil at room temperature and gradually cooling the mold temperature to around room temperature. After stopping the rotation, the molded product was taken out from the mold and subjected to the above evaluation. .

The symbols for each polycarbonate resin composition shown in Table 1 and the pulverization method are as follows. PC1: viscosity average molecular weight 1 produced by phosgene method
8,100 polycarbonate resin PC2: viscosity average molecular weight 2 produced by phosgene method
3,500 polycarbonate resin B1: Tris (2,4-di-tert-butylphenyl) phosphite (Irga, manufactured by Ciba-Geigy Japan)
fos168) B2: a compound of the following formula (13) produced based on the description in JP-A-3-77895. The purity of the compound was 73%.

[0107]

Embedded image

C1: Phenolic antioxidant (Irganox 1076, manufactured by Nippon Ciba Geigy Co., Ltd.) D1: Sulfur antioxidant (Sumilyzer TP-D, manufactured by Sumitomo Chemical Co., Ltd.) ST-1: Other phosphorus-based stabilizer (SANDOZ) Company San
dostab P-EPQ) ST-2: Other phosphorus-based stabilizer (T manufactured by Daihachi Chemical Co., Ltd.)
MP) UV1: Benzotriazole-based UV absorber (Chemisorb 79 manufactured by Chemipa Kasei Co., Ltd.) UV2: Benzotriazole-based UV absorber (ADEKA STAB LA-31 manufactured by Asahi Denka Kogyo KK) L1: Release agent (RIKEN Vitamin ( LIQUEMAR S-1
00A) L2: Release agent (Rikemar SL- manufactured by Riken Vitamin Co., Ltd.)
900) LS1: Bead-shaped crosslinked acrylic particles (MBX-5 [average particle size: 5 μm] manufactured by Sekisui Chemical Co., Ltd.) FL1: Fluorescent brightener (Hostalcus KS manufactured by Hoechst)
N) CL1: Dye (Macrolex Violet B manufactured by Bayer AG)

Pulverization method-Method A: The polycarbonate resin pellets were pulverized by a pulverizer, and the pulverized product was subjected to sieve classification. Pulverization method-Method B: Pulverization was performed with a pulverizer replaced with a pulverization blade having a longer use period than the pulverization blade used in Method A, and the pulverized product was subjected to the same sieve classification as PC-1.

[0110]

[Table 1]

As is evident from Table 1, when the viscosity-average molecular weight of the specific stabilizer of the present invention is used in combination, the injection-molded article molded under ordinary conditions can be obtained even when molded by rotational molding. It can be seen that they have the same hue. Further, it can be seen that the finish of the rotomolded product is affected by the distribution of the granular material.

[0112]

The polycarbonate resin particles of the present invention are particularly suitable for rotational molding. Rotational molding is particularly suitable for obtaining various types of glazing materials, lighting covers, large containers, etc., because large-sized molded products can be obtained with low distortion, especially for aircraft, ships, vehicles, and electronic and electrical equipment. It is suitably used in a wide range of fields such as mechanical devices.

[Brief description of the drawings]

FIG. 1 is a front view of a molded container.

FIG. 2 is a bottom side view of a molded container.

FIG. 3 is a diagram showing an outline of a screening test apparatus for whether text condition 3 is acceptable or not.

[Explanation of symbols]

 1 container-shaped molded product main body (open ball type; thickness of about 2 mm) 2 container-shaped molded product front center line (vertical direction) 3 molded product diameter (360 mm) 4 bottom-opened ball (opening) portion 5 bottom-opened ball (opening) ) Partial diameter (140 mm) 6 Round flask (500 ml) 7 Stirring motor 8 Thermometer (at the time of stirring, it is on the upper side) 9 Stirrer blade 10 Silicon oil bath 11 Sample powder and granules

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 69:00 C08L 69:00 F term (Reference) 4F070 AA50 AB22 AC01 AC04 AC06 AC13 AC16 AC22 AC27 AC28 AC39 AC40 AC45 AC50 AC55 AC75 AC76 AC79 AC83 AC84 AC85 AC88 AC90 AC92 AD01 AD02 AD03 AE01 AE03 AE05 AE06 AE07 AE17 AE23 DA11 DA21 DA41 DB09 DC07 DC11 4F071 AA50 AA81 AG31 BB13 BC04 BC07 4F205 AA28A AC04 AH55 A0473 GE01 GB01

Claims (3)

[Claims] 1. A powdery and granular material comprising a polycarbonate resin composition, wherein (1) its viscosity average molecular weight is 13,00
0-23,000, and (2) the particle size is Tyler
Polycarbonate resin particles obtained by a standard sieve method using a sieve, wherein particles having a size larger than 35 mesh are 3% by weight or less and particles having a size smaller than 150 mesh are 5% by weight or less. 2. The polycarbonate resin powder according to claim 1, wherein (3) particles having a size larger than 35 mesh determined by a standard sieving method after the test specified in the text satisfy a condition of 3% by weight or less. 3. A rotary molded article obtained by rotationally molding the polycarbonate resin particles according to claim 1.