JP6364977B2 - Polycarbonate resin composition pellets and method for producing the same - Google Patents

Description

  The present invention relates to a pellet of a glass fiber reinforced polycarbonate resin composition in which glass fiber is blended with a polycarbonate resin, a polycarbonate resin composition pellet which has improved mass productivity by preventing strand breakage during melt extrusion, The present invention relates to a polycarbonate resin molded product formed by molding a polycarbonate resin composition pellet.

  Polycarbonate resins are widely used in many fields as resins having excellent heat resistance, impact resistance, transparency, and the like. Among these, glass fiber reinforced polycarbonate resin compositions are excellent in characteristics such as dimensional stability, rigidity, and heat resistance, so that they are used in industries such as cameras, office automation equipment, communication equipment, precision equipment, electrical and electronic parts, automobile parts, and general machine parts. Widely used in the field.

However, characteristics such as dimensional stability, rigidity, and heat resistance of the glass fiber reinforced polycarbonate resin composition are better when the glass fiber content is large to some extent, but the glass fiber reinforced polycarbonate with a large glass fiber content is good. In a resin composition, for example, a polycarbonate resin composition with a high glass fiber content that contains 40% by mass or more of glass fiber, there is a problem that strand breakage is likely to occur during melt extrusion, and mass productivity is poor.
For this reason, in the past, glass fiber is highly filled at the expense of mass productivity, or the glass fiber blending amount is suppressed to ensure mass productivity.

  On the other hand, it is known that by adding silica particles to a thermoplastic resin, effects such as improved heat resistance, improved mechanical strength, and imparted flame retardancy can be obtained. Proposals have been made on surface treatments for improving the dispersibility of silica particles in thermoplastic resins. However, conventionally, there is no recognition that silica particles function to improve the dispersibility of glass fibers in polycarbonate resin.

JP 2012-214554 A JP 2011-89047 A

  As described above, in the conventional glass fiber reinforced polycarbonate resin composition, when the glass fiber blending amount is increased to increase the effect of improving various properties due to the glass fiber blending, strand breakage at the time of melt extrusion is likely to occur, and mass productivity is achieved. There was a problem that it would be inferior.

  The present invention solves this problem, and even a polycarbonate resin composition with high glass fiber filling can prevent occurrence of strand breakage during melt extrusion, and can be pelletized with excellent mass productivity. It is an object to provide a manufacturing method thereof and a molded product thereof.

  In the process of repeated studies to solve the above-mentioned problems, the inventors of the present invention are likely to cause localized breakage of glass fibers in the resin composition due to strand breakage during melt extrusion in the glass fiber-reinforced polycarbonate resin composition. Thus, it was presumed that the strand breakage was generated from the localized location of the glass fiber, and in order to prevent the occurrence of the localized location of the glass fiber, studies were made to increase the dispersibility of the glass fiber. As a result, it is possible to improve the dispersibility of the glass fiber in the polycarbonate resin by blending silica particles having a specific particle size with a predetermined ratio with respect to the glass fiber. Are mixed in advance and then melt-kneaded with other components such as polycarbonate resin, so that even better dispersibility improvement effect can be obtained. As a result, the occurrence of strand breakage during melt extrusion is effective. It was found that it can be prevented.

  The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] (A) 45 to 75 parts by mass of polycarbonate resin and (B) 55 to 25 parts by mass of glass fiber so as to be a total of 100 parts by mass, and (C) having an average particle size of 30 to 300 nm A pellet of a polycarbonate resin composition containing 0.01 to 1 part by mass of silica particles with respect to 100 parts by mass of (B) glass fiber, and (B) glass fibers and (C) silica particles are mixed in advance. A polycarbonate resin composition pellet obtained by melting and kneading the mixture with (A) a polycarbonate resin and pelletizing the obtained polycarbonate resin composition.

[ 2 ] A method for producing the polycarbonate resin composition pellets according to [1 ] using an extruder, wherein the mixture of (B) glass fiber and (C) silica particles is extruded by a side feed method. A method for producing a polycarbonate resin composition pellet, which is supplied from the middle of the process and melt-kneaded and then pelletized.
[3] (C) Silica containing 45 to 75 parts by mass of (A) polycarbonate resin and 55 to 25 parts by mass of (B) glass fiber so as to be a total of 100 parts by mass, and (C) silica having an average particle size of 30 to 300 nm A method of producing pellets of a polycarbonate resin composition containing 0.01 to 1 part by mass of particles (B) with respect to 100 parts by mass of glass fibers, wherein (B) glass fibers and (C) silica particles are mixed in advance And (A) a polycarbonate resin composition, and the resulting polycarbonate resin composition is pelletized.
[4] A method for producing the polycarbonate resin composition pellets using an extruder according to [3], wherein the mixture of (B) glass fibers and (C) silica particles is extruded by a side feed method. A method for producing a polycarbonate resin composition pellet, which is supplied from the middle of the process and melt-kneaded and then pelletized.

According to the present invention, even a polycarbonate resin composition with high glass fiber filling can prevent strand breakage during melt extrusion and can be pelletized with excellent mass productivity.
According to the present invention, high-filling of glass fibers is possible without impairing mass productivity, and high-filling glass fibers are excellent in various properties such as dimensional stability, rigidity, and heat resistance, and are also excellent in productivity. Resin composition pellets and molded articles thereof can be provided.

  Hereinafter, embodiments of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

  The polycarbonate resin composition pellets of the present invention include (A) 45 to 75 parts by mass of polycarbonate resin and (B) 55 to 25 parts by mass of glass fibers so that the total amount becomes 100 parts by mass, and further has an average particle size of 30. A pellet of a polycarbonate resin composition containing 0.01 to 10 parts by mass of (C) silica particles of ~ 1000 nm with respect to 100 parts by mass of (B) glass fibers, wherein (B) glass fibers and (C) silica particles A mixture obtained by previously mixing (A) with a polycarbonate resin is melt-kneaded, and the resulting polycarbonate resin composition is pelletized.

  The polycarbonate resin molded product of the present invention is formed by molding such a polycarbonate resin composition pellet of the present invention.

  Moreover, the manufacturing method of the polycarbonate resin composition pellets of the present invention, when manufacturing the polycarbonate resin composition pellets of the present invention using an extruder, the mixture of (B) glass fiber and (C) silica powder, It is characterized in that it is fed from the middle of the extruder by the side foot method, melt-kneaded and then pelletized.

  In the following, the polycarbonate resin composition constituting the polycarbonate resin composition pellet of the present invention is referred to as “the polycarbonate resin composition of the present invention”.

[(A) Polycarbonate resin]
As the polycarbonate resin (A) used in the polycarbonate resin composition of the present invention, any conventionally known polycarbonate resin can be used. Examples of the polycarbonate resin (A) include aromatic polycarbonate resins, aliphatic polycarbonate resins, and aromatic-aliphatic polycarbonate resins, and aromatic polycarbonate resins are preferable.

  The aromatic polycarbonate resin is an optionally branched aromatic polycarbonate polymer obtained by reacting an aromatic hydroxy compound with a phosgene or carbonic acid diester. The method for producing the aromatic polycarbonate resin is not particularly limited, and may be a conventional method such as a phosgene method (interfacial polymerization method) or a melting method (transesterification method). Further, it may be a polycarbonate resin produced by a melting method and produced by adjusting the amount of OH groups of terminal groups.

Typical examples of the aromatic dihydroxy compound that is one of the raw materials of the aromatic polycarbonate resin used in the present invention include, for example, bis (4-hydroxyphenyl) methane and 2,2-bis (4-hydroxyphenyl). Propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, bis (4- Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone and the like.
Further, polyhydric phenols having 3 or more hydroxy groups in the molecule such as 1,1,1-tris (4-hydroxylphenyl) ethane, 1,3,5-tris (4-hydroxyphenyl) benzene, etc. are branched. A small amount can be used in combination as an agent.
Among these aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferable. These aromatic dihydroxy compounds can be used alone or in admixture of two or more.

  In order to obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tris ( 4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-3, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1 -Polyhydroxy compounds such as tris (4-hydroxyphenyl) ethane, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloruisatin, 5,7-dichloroisatin, 5-bromoisatin, etc. May be used as a part of the aromatic dihydroxy compound, and the amount used thereof may be And from 0.01 to 10 mol% against, and preferably 0.1 to 2 mol%.

  In the polymerization by the transesterification method, a carbonic acid diester is used as a monomer instead of phosgene. Representative examples of the carbonic acid diester include substituted diaryl carbonates typified by diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates typified by dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate and the like. These carbonic acid diesters can be used alone or in admixture of two or more. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable.

  Moreover, said carbonic acid diester may substitute the quantity of the 50 mol% or less preferably 30 mol% or less with the dicarboxylic acid or dicarboxylic acid ester preferably. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

  When an aromatic polycarbonate resin is produced by a transesterification method, a catalyst is usually used. Although there is no limitation on the catalyst species, generally basic compounds such as alkali metal compounds, alkaline earth metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds are used. Of these, alkali metal compounds and / or alkaline earth metal compounds are particularly preferred. These may be used alone or in combination of two or more. In the transesterification method, the polymerization catalyst is generally deactivated with p-toluenesulfonic acid ester or the like.

  (A) A preferable polycarbonate resin is an aromatic polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane or 2,2-bis (4-hydroxyphenyl) propane and another aromatic dihydroxy compound. And aromatic polycarbonate copolymers derived from the above. Further, for the purpose of imparting flame retardancy and the like, a polymer or oligomer having a siloxane structure can be copolymerized. (A) The polycarbonate resin may be a mixture of two or more polymers and / or copolymers of different raw materials, and may have a branched structure up to 0.5 mol%.

  The terminal hydroxyl group content of the (A) polycarbonate resin such as an aromatic polycarbonate resin has a great influence on the thermal stability, hydrolysis stability, color tone and the like. In order to give practical physical properties, the terminal hydroxyl group content of the (A) polycarbonate resin is usually 30 to 2000 ppm, preferably 100 to 1500 ppm, more preferably 200 to 1000 ppm. As the end-capping agent to be adjusted, p-tert-butylphenol, phenol, cumylphenol, p-long chain alkyl-substituted phenol or the like can be used.

  As the amount of residual monomer in the polycarbonate resin (A) such as aromatic polycarbonate resin, the aromatic dihydroxy compound is 150 ppm or less, preferably 100 ppm or less, more preferably 50 ppm or less. When synthesized by the transesterification method, the residual amount of carbonic acid diester is 300 ppm or less, preferably 200 ppm or less, more preferably 150 ppm or less.

  The molecular weight of the (A) polycarbonate resin such as aromatic polycarbonate resin is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 20 ° C. using methylene chloride as a solvent, and preferably in the range of 10,000 to 50,000. More preferably, it is a thing of 10,000-40,000, Especially preferably, it is a thing of the range of 12,000-30,000. By setting the viscosity average molecular weight to 10,000 or more, the mechanical properties are more effectively exhibited, and by setting the viscosity average molecular weight to 50,000 or less, the molding process becomes easier. Further, two or more kinds of polycarbonate resins having different viscosity average molecular weights may be mixed, or a polycarbonate resin having a viscosity average molecular weight outside the above preferred range may be mixed to be within the above molecular weight range.

  Furthermore, the (A) polycarbonate resin used in the present invention may be not only a polycarbonate resin as a virgin raw material but also a polycarbonate resin regenerated from a used product, a so-called material recycled polycarbonate resin. Used products include optical recording media such as optical disks, light guide plates, automobile window glass and automobile headlamp lenses, vehicle transparent members such as windshields, containers such as water bottles, glasses lenses, soundproof walls and glass windows, waves A building member such as a plate is preferred. Further, the form of the recycled polycarbonate resin is not particularly limited, and any non-conforming product, pulverized product such as sprue or runner, and pellets obtained by melting them can be used.

[(B) Glass fiber]
As the (B) glass fiber used in the present invention, any glass fiber made of alkali-free glass (E glass) can be used as long as it is usually used in thermoplastic resins. (B) It is preferable that the average fiber length of glass fiber is 1-10 mm, and a fiber diameter is 5-20 micrometers.

  When the average fiber length of the (B) glass fiber used in the present invention exceeds the above upper limit value, the glass fiber is liable to drop off from the surface of the molded product, and the appearance of the molded product tends to be inferior. If it is less than the value, the glass fiber has a small aspect ratio, so the effect of improving the mechanical strength is insufficient. Similarly, when the average fiber diameter of the glass fibers is less than the lower limit, the effect of improving the mechanical strength is insufficient, and when the upper limit is exceeded, the appearance of the molded product is deteriorated. The average fiber length of the glass fiber is preferably 1 to 7 mm, and the average fiber diameter is preferably 7 to 15 μm.

  In addition, (B) The average fiber length and average fiber diameter of the glass fiber are determined as the average value of the fiber length and fiber diameter measured for about 100 glass fibers arbitrarily selected by SEM (scanning electron microscope) observation. However, catalog values can be adopted for commercial products.

  The glass fiber (B) used in the present invention may be subjected to a surface treatment with a silane coupling agent such as aminosilane or epoxysilane for the purpose of improving the adhesion with the (A) polycarbonate resin. Further, for the purpose of improving the melt heat stability of the polycarbonate resin composition, it may be used after being treated with phosphorous acid.

  For the phosphorous acid treatment of glass fiber, any conventionally known method may be used. For example, the method described in Japanese Patent No. 2830186 may be mentioned. Among them, a method in which glass fibers are put into an aqueous phosphorous acid solution and water is evaporated while heating and stirring is preferable.

[(A) Compounding ratio of polycarbonate resin and (B) glass fiber]
In this invention, it uses in the ratio of (B) glass fiber 55-25 mass parts with respect to (A) polycarbonate resin 45-75 mass parts (however, it is the sum total of (A) polycarbonate resin and (B) glass fiber. 100 parts by mass).

  When the ratio of (A) polycarbonate resin and (B) glass fiber is within the above range, the effect of improving various properties by blending (B) glass fiber can be sufficiently obtained while securing mass productivity. (A) When polycarbonate resin is more than the above upper limit value and (B) glass fiber is less than the above lower limit value, (B) the effect of improving various properties such as dimensional stability, rigidity, and heat resistance by glass fiber blending is sufficient. Can't get to. Further, the present invention is effective in preventing strand breaks during melt extrusion in high filling of glass fibers, and (B) when the glass fiber content is less than the above lower limit value, strand breaks during melt extrusion are unlikely to occur. The remarkable effect of the present invention is difficult to obtain. Conversely, when (A) the polycarbonate resin is less than the above lower limit value and (B) the glass fiber is more than the above upper limit value, even if (C) silica particles are blended, strand breakage during melt extrusion cannot be prevented. Further, the fluidity of the resin composition is lowered, the appearance of the molded product is also lowered, and the glass fibers are easily dropped from the surface of the molded product.

  (A) The more preferable mixture ratio of polycarbonate resin and (B) glass fiber is (B) glass fiber 50-30 mass parts with respect to (A) polycarbonate resin 50-70 mass parts (however, (A) polycarbonate The total of the resin and (B) glass fiber is 100 parts by mass.)

[(C) Silica particles]
The (C) silica particles used in the present invention are silica particles having an average particle size of 30 to 1000 nm.
Such (C) silica particles are uniformly dispersed in the polycarbonate resin composition, and (B) are uniformly dispersed and adhered on the glass fiber or the resin particle, and the fiber-fiber, fiber-particle, particle -Demonstrating the bearing function between the particles, (B) glass fiber (A) high fluidization in the polycarbonate resin to suppress agglomeration and enhance dispersibility, causing strand breakage during melt extrusion (B) Generation | occurrence | production of the localized location of glass fiber is prevented. In particular, in the present invention, (C) silica particles are melt-kneaded as a mixture obtained by previously mixing (B) glass fibers and (C) silica particles, so that the bearing effect of (C) silica particles is even more effective. As a result of this effect acting directly on the glass fiber (B), an excellent effect of improving dispersibility is obtained. That is, if (C) silica particles and (B) glass fibers are mixed in advance, (C) silica particles adhere to the surface of (B) glass fibers, and (B) the glass fibers are already melted and kneaded. It is in a sufficiently loosened state, and (A) is rapidly dispersed uniformly in the resin composition during melt kneading with other components such as polycarbonate resin.

  (C) The larger the average particle size of the silica particles, the better the bearing effect. However, silica particles having an excessively large average particle size tend to lower the mechanical strength. For this reason, the average particle diameter of (C) silica particles is 30 to 1000 nm, preferably 30 to 300 nm, and more preferably 50 to 250 nm.

  In addition, the (C) silica particles are preferably subjected to a surface treatment as described in the above-mentioned Patent Documents 1 and 2 in order to improve dispersibility and adhesion in the resin composition. Suitable surface treatments include, for example, phenyltrimethoxysilane, vinyltrimethoxysilane, epoxytrimethoxysilane, methacryltrimethoxysilane, aminotrimethoxysilane, ureidotrimethoxysilane, mercaptotrimethoxysilane, isocyanate trimethoxysilane, acrylic Trimethoxysilane, more specifically phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3- Surface treatment with a silane coupling agent such as acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, preferably this silane coupling agent, tetramethyldisilazane, hexamethyldisilazane, pentamethyldisilane Surface treatment using an organosilazane such as silazane, the above silane coupling agent, methyltrimethoxysilane, methyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltri The surface treatment using together with other silane coupling agents, such as ethoxysilane, etc. are mentioned.

  In this invention, (C) silica particle is 0.01-10 mass parts with respect to 100 mass parts of (B) glass fiber, Preferably it is 0.01-2 mass parts, More preferably, it is 0.025-1 mass. Use parts. (B) If the ratio of (C) silica particles to glass fibers is less than the above lower limit value, the effect of the present invention by blending (C) silica particles cannot be sufficiently obtained, and if the above upper limit value is exceeded, Mechanical strength may be impaired, and the amount of expensive (C) silica particles used is increased, resulting in high raw material costs.

  In the present invention, (C) silica particles are melt-kneaded into the polycarbonate resin composition of the present invention as a mixture obtained by previously mixing (B) glass fibers and (C) silica particles.

<Other ingredients>
The polycarbonate resin composition of the present invention, other than the above (A) polycarbonate resin, (B) glass fiber, and (C) silica particles, as long as it does not significantly impair the performance, in order to obtain desired physical properties. Other components may be blended. Other components include, for example, stabilizers such as UV absorbers, antioxidants, heat stabilizers, additives such as pigments, dyes, lubricants, flame retardants, anti-dripping agents, mold release agents, slidability improvers, An elastomer or the like can be blended. The polycarbonate resin composition of the present invention can also contain (A) a thermoplastic resin other than the polycarbonate resin.

<Other thermoplastic resins>
(A) The kind and compounding quantity of thermoplastic resins other than polycarbonate resin can be suitably selected for the purpose of improving performance such as moldability and chemical resistance. (A) As thermoplastic resins other than polycarbonate resin, polyester resin, polyamide resin, polyolefin resin, polyphenylene ether resin, styrene resin, polysulfone, polyethersulfone, polyphenylene sulfide, polyacrylate, polyamideimide, polyetherimide, etc. Is mentioned.

  Examples of the polyester resin include polybutylene terephthalate, polyethylene terephthalate, polybutylene naphthalate, and polyethylene naphthalate. Examples of the polyolefin resin include polyethylene and polypropylene. Examples of the polyphenylene ether resins include polyphenylene ether resins and mixed resins of polyphenylene ether and polystyrene and / or HIPS (impact polystyrene). Examples of the styrene resin include polystyrene, HIPS, AS resin, ABS resin, and the like. (A) The thermoplastic resin other than the polycarbonate resin preferably includes polybutylene terephthalate, polyethylene terephthalate, polyphenylene ether resin, HIPS, AS resin, ABS resin and the like. The blending amount of the thermoplastic resin other than (A) polycarbonate resin is preferably less than 50% by mass of the total amount of (A) polycarbonate resin and (A) thermoplastic resin other than polycarbonate resin, more preferably 40% by mass. % Or less, and most preferably 30% by mass or less.

<Antioxidant>
Examples of the antioxidant include hindered phenolic antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(me Citylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol, etc. These may be used in combination of two or more.

  Among the above, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate is preferred. These two phenolic antioxidants are commercially available from Ciba Specialty Chemicals under the names “Irganox 1010” and “Irganox 1076”.

  When using antioxidant, the compounding quantity is 0.001-1 mass part normally with respect to 100 mass parts of (A) polycarbonate resin, Preferably it is 0.01-0.5 mass part. When the blending amount of the antioxidant is less than 0.001 part by mass, the effect as an antioxidant is insufficient, and when it exceeds 1 part by mass, the effect reaches a peak and is not economical.

<Heat stabilizer>
As the heat stabilizer, at least one ester in the molecule is esterified with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms, phosphorous acid ester compound, phosphorous acid, and tetrakis ( And at least one selected from the group of 2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphonite.

  Specific examples of the phosphite compound include trioctyl phosphite, tridecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, tris (octylphenyl) phosphite, tris (2,4-di-). tert-butylphenyl) phosphite, tridecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, Distearyl pentaerythritol diphosphite, diphenylpentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Sphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol di Examples thereof include phosphite and bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite. These may be used alone or in admixture of two or more. Among the above, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert) -Butyl-4-methylphenyl) pentaerythritol diphosphite is preferred.

  When using a heat stabilizer, the compounding quantity is 0.001-1 mass part normally with respect to 100 mass parts of (A) polycarbonate resin, Preferably it is 0.01-0.5 mass part. When the blending amount of the heat stabilizer is less than 0.001 part by mass, the effect as the heat stabilizer is insufficient, and when it exceeds 1 part by mass, the hydrolysis resistance may deteriorate.

<Release agent>
The release agent includes at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, and polysiloxane silicone oil. Can be mentioned.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, the same one as the aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or polyhydric alcohol having 30 or less carbon atoms is more preferable. Here, aliphatic includes alicyclic compounds. Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  In addition, said ester compound may contain aliphatic carboxylic acid and / or alcohol as an impurity, and may be a mixture of a some compound.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, as the aliphatic hydrocarbon, alicyclic hydrocarbon is also included. Moreover, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable. The number average molecular weight of the aliphatic hydrocarbon is preferably 200 to 5,000. These aliphatic hydrocarbons may be a single substance, or may be a mixture of various constituent components and molecular weights, as long as the main component is within the above range.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

  When using a mold release agent, the compounding quantity is 0.001-10 mass parts normally with respect to 100 mass parts of (A) polycarbonate resin, Preferably it is 0.01-1 mass part. When the blending amount of the release agent is less than 0.001 part by mass, the effect of releasability may not be sufficient, and when it exceeds 10 parts by mass, the hydrolysis resistance is deteriorated and the mold is contaminated during injection molding. There are problems such as.

<Ultraviolet absorber>
Specific examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds in addition to inorganic ultraviolet absorbers such as cerium oxide and zinc oxide. Of these, organic ultraviolet absorbers are preferred. In particular, benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2, 4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazine-4- ON], [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester is preferred.

  Specific examples of the benzotriazole compound include condensates of methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol. Specific examples of other benzotriazole compounds include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy- 3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methyl Ren-bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-tert-butyl-5- (2H- Benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate. Two or more of these may be used in combination.

  Of the above, preferably 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl]- 2H-benzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl)- 6- (2N-benzotriazol-2-yl) phenol].

  When using a ultraviolet absorber, the compounding quantity is 0.01-3 mass parts normally with respect to 100 mass parts of (A) polycarbonate resin, Preferably it is 0.1-1 mass part. When the blending amount of the ultraviolet absorber is less than 0.01 parts by mass, the effect of improving weather resistance may be insufficient, and when it exceeds 3 parts by mass, problems such as mold deposit may occur.

<Dye and pigment>
Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; zinc white, petal, chromium oxide, titanium oxide, iron black, titanium yellow, and zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments. Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, and isoindolinone. And condensed polycyclic dyes such as quinophthalone; anthraquinone, heterocyclic, and methyl dyes and the like. Two or more of these may be used in combination. Among these, carbon black, titanium oxide, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.

  When using a dye and pigment, the compounding quantity is 5 mass parts or less normally with respect to 100 mass parts of (A) polycarbonate resin, Preferably it is 3 mass parts or less, More preferably, it is 2 mass parts or less. When the amount of the dye / pigment exceeds 5 parts by mass, the impact resistance may not be sufficient.

<Flame Retardant>
Examples of the flame retardant include halogenated bisphenol A polycarbonate, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, halogenated flame retardant such as brominated polystyrene, phosphate ester flame retardant, diphenylsulfone-3,3 ′. -Organic metal salt flame retardants such as dipotassium disulfonate, potassium diphenylsulfone-3-sulfonate, potassium perfluorobutanesulfonate, and polyorganosiloxane flame retardants are preferable, but phosphate ester flame retardants are particularly preferable. .

  Specific examples of the phosphate ester flame retardant include triphenyl phosphate, resorcinol bis (dixylenyl phosphate), hydroquinone bis (dixylenyl phosphate), 4,4′-biphenol bis (dixylenyl phosphate), bisphenol A Examples thereof include bis (dixylenyl phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), 4,4′-biphenol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like. Two or more of these may be used in combination. In these, resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are preferable.

  When using a flame retardant, the compounding quantity is 1-30 mass parts normally with respect to 100 mass parts of (A) polycarbonate resin, Preferably it is 3-25 mass parts, More preferably, it is 5-20 mass parts. When the blending amount of the flame retardant is less than 1 part by mass, the flame retardancy may not be sufficient, and when it exceeds 30 parts by mass, the heat resistance may decrease.

<Anti-dripping agent>
Examples of the anti-dripping agent include fluorinated polyolefins such as polyfluoroethylene, and polytetrafluoroethylene having fibril forming ability is particularly preferable. This shows the tendency to disperse | distribute easily in a polymer and to couple | bond together polymers and to make a fibrous material. Polytetrafluoroethylene having fibril-forming ability is classified as type 3 according to the ASTM standard. Polytetrafluoroethylene can be used in solid form or in the form of an aqueous dispersion. Examples of polytetrafluoroethylene having fibril-forming ability include “Teflon (registered trademark) 6J” or “Teflon (registered trademark) 30J” from Mitsui DuPont Fluorochemical Co., Ltd. and “Polyflon (trade name) from Daikin Industries, Ltd. Is commercially available.

  When using a dripping inhibitor, the compounding quantity is 0.02-4 mass parts normally with respect to 100 mass parts of (A) polycarbonate resin, Preferably it is 0.03-3 mass parts. When the compounding amount of the dripping inhibitor exceeds 5 parts by mass, the appearance of the molded product may be deteriorated.

[Production method of polycarbonate resin composition pellets]
The kneading conditions for producing the polycarbonate resin composition pellets of the present invention differ depending on the types and blending ratios of the components used in the polycarbonate resin composition, and cannot be generally stated. Among the blending components, (B) glass fibers and (C) silica particles are melt-kneaded with other components as a mixture obtained by mixing them in advance. Preferably, this mixture is supplied from the middle of the extruder to a melt-kneaded product in which other components such as polycarbonate resin are sufficiently melt-kneaded using a side feed method when melt-kneading using an extruder. Melt and knead. The (C) silica particles premixed with the (B) glass fiber may be the total amount of the (C) silica particles used in the production of the polycarbonate resin composition of the present invention, and a part thereof, the remainder being (A) The resin composition may be mixed with the polycarbonate resin and supplied from the hopper of the extruder. (C) In order to more effectively obtain the effect of improving the dispersibility of the (B) glass fiber by the silica particles, the polycarbonate resin composition It is preferable to mix 50% by mass or more, particularly preferably the total amount of all (C) silica particles used in the production of (B) with the total amount of (B) glass fiber and side feed.

Conventionally, when glass fibers are blended, glass fibers are added by a side feed method in order to prevent cutting and bending of the glass fibers during melt kneading. In the present invention, not only glass fibers, but also (B) glass fibers and (C) silica particles are side-fed to cause (C) silica particles to adhere to the surface of (B) glass fibers in advance (B A high dispersion effect can be obtained by supplying the mixture in which the dispersibility of the glass fiber is sufficiently enhanced into the kneaded product in which (A) other components such as the polycarbonate resin are sufficiently melt-kneaded.
In this case, since the mixture of (B) glass fiber and (C) silica particles is preferably supplied in a state in which the resin component is sufficiently melt-kneaded, in this respect, side feed is performed on the downstream side of the extruder. However, if the side feed position is excessively downstream, the mixture is extruded before being sufficiently dispersed in the resin composition. From such a point of view, the mixture of (B) glass fiber and (C) silica particles is particularly located on the downstream side of the barrel length L from about 1/5 to 4/5 from the upstream side (hopper part) of the extruder. It is preferable to ensure a melt-kneading time of 5 to 120 seconds after feeding and side-feeding the mixture. In addition, there is no restriction | limiting in particular about L / D (barrel length / screw diameter) of the extruder used for melt extrusion, and it is about 25-50 normally. Moreover, it is preferable to set screw rotation speed to 150-600 rpm and cylinder temperature to about 250-300 degreeC.

[Polycarbonate resin molded product]
The polycarbonate resin composition pellets of the present invention are used as resin materials for various products (molded products) and manufacturing (molding). As a molding method, a conventionally known method of molding a molded product from a thermoplastic resin material can be applied without limitation. Specifically, general injection molding methods, ultra-high speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist, molding methods using heat insulating molds, rapid heating molds Examples of the molding method used include foam molding (including supercritical fluid), insert molding, in-mold coating (IMC) molding method, extrusion molding method, sheet molding method, thermoforming method, and press molding method.

Further, the polycarbonate resin composition of the present invention can be subjected to multicolor composite molding with other thermoplastic resin compositions to form composite molded products.
The polycarbonate resin molded product of the present invention has various characteristics such as excellent dimensional stability, rigidity, and heat resistance due to high filling of glass fiber and mass productivity, so that it can be used for cameras, office automation equipment, communication equipment, precision equipment, electrical and electronic parts, automobile parts. It can be suitably used for various products such as general machine parts, and is particularly suitable as a camera, OA equipment, electrical / electronic parts, and automobile parts.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded.

[Materials used]
The raw material components used in the following examples , reference examples and comparative examples are as follows.

<(A) Polycarbonate resin>
"Iupilon (registered trademark) S-3000" manufactured by Mitsubishi Engineering Plastics Co., Ltd. (bisphenol A type aromatic polycarbonate resin produced by interfacial polymerization method, viscosity average molecular weight: 21,500)

<(B) Glass fiber>
“T187H” manufactured by Nippon Electric Glass Co., Ltd. (average fiber diameter 10 μm, average fiber length 3.0 mm)

<(C) Silica particles>
Silica particles (C-1): Silica manufactured by Admatechs Co., Ltd., average particle size 10 nm,
Phenylsilane surface-treated product Silica particles (C-2): Silica manufactured by Admatechs Co., Ltd., average particle size 50 nm,
Phenylsilane surface-treated product Silica particles (C-3): Silica manufactured by Admatechs Co., Ltd., average particle size 100 nm,
Phenylsilane surface-treated product Silica particles (C-4): Silica manufactured by Admatechs Co., Ltd., average particle size 250 nm,
Phenylsilane surface-treated product Silica particles (C-5): Silica manufactured by Admatechs Co., Ltd., average particle size 500 nm,
Phenylsilane surface treatment product

[Examples 1-5 , 8-12 , 14-16 , Reference Examples 6, 7, 13, 17, Comparative Examples 1-6]
Polycarbonate resin composition pellets were produced by the melt kneading method shown in Tables 1 and 2 with the formulations shown in Tables 1 and 2.
In the case of the melt kneading method A, (B) glass fibers and (C) silica particles are uniformly mixed in advance by a tumbler mixer, and (A) the polycarbonate resin is melt-kneaded by feeding it from an hopper to an extruder. The mixture of B) glass fiber and (C) silica particles was side-fed.
As the extruder, a twin-screw extruder manufactured by Nippon Steel Works (TEX30HSST, L / D = 42) was used, and melt extrusion was carried out under conditions of a screw rotation speed of 200 rpm, a cylinder temperature of 300 ° C., and a discharge rate of 20 kg / hr. The strands were rapidly cooled in a water bath and pelletized using a pelletizer. The mixture of (B) glass fiber and (C) silica particles was side-fed from the downstream position of 2/3 of the barrel length L from the upstream side of the extruder. The melt-kneading time after side feeding was 15 seconds.

  In the case of melt kneading method B, (B) only glass fibers are side-feeded to the extruder, and (C) silica particles are melted except that they are mixed with (A) polycarbonate resin and fed from the hopper of the extruder. It carried out similarly to the kneading method A.

The melt extrudability at this time was determined as the number of times the strand was naturally cut after the strand was guided to a pelletizer and stabilized when 6 kg of the resin composition was melt extruded, and evaluated according to the following criteria.
○: No strand break or 2 or less strand breaks Δ: 3 to 5 strand breaks ×: 6 or more strand breaks

  Further, the obtained polycarbonate resin composition pellets were dried at 120 ° C. for 5 hours, and then, with an injection molding machine (“J50EP” manufactured by Nippon Steel), the cylinder temperature was 300 ° C., the mold temperature was 110 ° C., and the molding cycle was 50 seconds. The ISO multi-purpose test piece (4 mm thickness) was produced under the conditions described above, and the following evaluations were performed. Tables 1 and 2 show the evaluation results.

<Bending test>
In accordance with ISO178, bending strength and bending elastic modulus were measured.
<Charpy impact strength>
In accordance with ISO 179-1 & 2, 3t Charpy impact strength (without notch and with notch) was measured.

Tables 1 and 2 show the following.
In Comparative Examples 3 and 6 in which (C) silica particles are not blended and in Comparative Examples 1 and 2 in which the average particle size is too small even if (C) silica particles are blended, there is a problem of strand breakage. Even if (C) silica particles having an appropriate average particle diameter are blended, in Comparative Examples 4 and 5 in which (B) glass fibers and (C) silica particles are not previously melt-kneaded as a mixture, there is a problem of strand breakage. is there.
On the other hand , in Examples 1 to 5 , 8 to 12 , and 14 to 16 in which a mixture of (B) glass fiber and (C) silica particles was side-fed, strand breakage was prevented, and pellets of a polycarbonate resin composition Can be manufactured stably.
Further, from the comparison between Comparative Example 3 and Examples 1 to 5 , 8 , and 9 and the comparison between Comparative Example 6 and Examples 10 to 12 , (C) the combination of silica particles, particularly the high combination of silica particles having a large particle size. Although the mechanical strength tends to decrease slightly, it can be seen that (C) a decrease in mechanical strength can be suppressed by appropriately selecting the average particle size and blending amount of the silica particles.

Claims (4)

(A) 45 to 75 parts by mass of polycarbonate resin and (B) 55 to 25 parts by mass of glass fiber so as to be a total of 100 parts by mass, and (C) silica particles having an average particle size of 30 to 300 nm. (B) A pellet of a polycarbonate resin composition containing 0.01 to 1 part by mass with respect to 100 parts by mass of glass fiber,
(B) A polycarbonate resin composition obtained by melting and kneading a mixture of glass fibers and (C) silica particles in advance with (A) a polycarbonate resin and pelletizing the obtained polycarbonate resin composition Pellets. A process for producing a polycarbonate resin composition pellets according to claim 1 with an extruder, the (B) mixture of glass fibers and (C) silica particles, in the middle of the extruder in the side feed method A process for producing a polycarbonate resin composition pellet, characterized in that the pellet is pelletized after being supplied and melt-kneaded. (A) 45 to 75 parts by mass of polycarbonate resin and (B) 55 to 25 parts by mass of glass fiber so as to be 100 parts by mass in total, and further (C) silica particles having an average particle size of 30 to 300 nm ( B) A method for producing a pellet of a polycarbonate resin composition containing 0.01 to 1 part by mass with respect to 100 parts by mass of glass fiber,
(B) A polycarbonate resin composition comprising a mixture of glass fiber and (C) silica particles previously mixed with (A) a polycarbonate resin and pelletizing the resulting polycarbonate resin composition. Pellet manufacturing method. In Claim 3, It is a method of manufacturing the said polycarbonate resin composition pellet using an extruder, Comprising: The mixture of the said (B) glass fiber and (C) silica particle is carried out from the middle of an extruder by the side feed method. A process for producing a polycarbonate resin composition pellet, characterized in that the pellet is pelletized after being supplied and melt-kneaded.