JP5111456B2 - Method for using aromatic polycarbonate resin composition for exterior material of OA equipment or home appliance - Google Patents

Description

  The present invention relates to a method of using an aromatic polycarbonate resin composition as an exterior material for OA equipment or home appliances. More specifically, a resin composition comprising a specific ratio of an aromatic polycarbonate resin, polylactic acid and an impact modifier, and a resin composition of an aromatic polycarbonate resin and an ABS resin (acrylonitrile-butadiene-styrene copolymer resin). An aromatic polycarbonate resin composition having impact resistance and molding processability (fluidity) comparable to those of the resin composition, excellent heat resistance and hue of the molded product, and reduced environmental load Is used for the exterior material of OA equipment or home appliances. Furthermore, the present invention is a resin composition comprising a specific ratio of an aromatic polycarbonate resin, polylactic acid, an impact modifier and a flame retardant (particularly a phosphate ester flame retardant), and is often required for materials for electrical and electronic equipment. The present invention relates to a method for using an aromatic polycarbonate resin composition having the above-mentioned properties while having high flame retardancy, as an exterior material for OA equipment or home appliances.

  Aromatic polycarbonates with carbonate ester bonds as repeating units generally have excellent heat resistance, mechanical properties, impact resistance, flame retardancy, dimensional stability, etc., OA equipment field, automotive field, electric / electronic Widely used in applications such as the parts field. Furthermore, a resin composition of an aromatic polycarbonate resin and an ABS resin is used in a wide range of fields by taking advantage of its excellent moldability (fluidity) and impact resistance. However, the resin composition is generally inferior in hue, depending on the type and blending amount of the ABS resin. The cause of such poor hue is that polybutadiene contains an unsaturated bond, impurities (emulsifier and coagulant) contained in the polymerization are factors that induce thermal degradation of the bond, and such impurities The aromatic polycarbonate resin also has an adverse effect on the thermal decomposition. On the other hand, in recent years, various colors have been required for molded articles, and in this respect, the hue of the resin composition is desired to have higher brightness. In particular, when performing coating with a weak hiding power such as a metallic system, it is desirable that the molded product on the side to be coated has the same color tone. Of course, by repeating the coating process to increase the thickness of the coating film, the color tone of the molded product is not a problem, but a plurality of coating processes are not preferable in terms of cost and environmental load.

In many fields where aromatic polycarbonate resins are applied, reuse is one of the important issues. However, problems such as thermal decomposition and deterioration of hue in the resin composition of the aromatic polycarbonate resin and the ABS resin are generally remarkable in the recycled aromatic polycarbonate resin. This is because the aromatic polycarbonate resin to be reused contains not a few factors that cause defects such as deterioration over time and mixing of other foreign matters. If a resin composition having a good hue (generally having a high lightness) is obtained, it can be used in a wider range, and the reuse efficiency of the aromatic polycarbonate resin can be improved.
Furthermore, while there is the above-mentioned demand, there is an increasing trend to demand materials with low environmental impact in many fields where aromatic polycarbonate resins are applied, and materials are being evaluated from the viewpoint of life cycle assessment. However, not only aromatic polycarbonates, but also general-purpose plastics and engineering plastics are all made of petroleum-derived compounds. Therefore, if the material exhibits the same performance, a material containing a non-petroleum resource material may be required as a material with a small environmental load.

Polylactic acid is a plant-derived plastic among biodegradable plastics, has a lower environmental impact than other petroleum-derived biodegradable plastics, and has a relatively high heat resistance among biodegradable plastics. In some cases, its uses are expanding. However, the present situation is that there is not yet sufficient knowledge for application to materials for electrical and electronic equipment, in which particularly high flame retardancy is often required.
It is known to blend a natural polymer such as corn starch with an aromatic polycarbonate resin (see Patent Document 1), a resin composition of polylactic acid and an aromatic polycarbonate resin, and the resin composition has a good pearly luster. It is also known to have excellent fluidity, heat resistance, rigidity and the like (see Patent Document 2). Furthermore, it is also known that a resin composition in which polylactic acid and an aliphatic polycarbonate are mixed, and that the resin composition has transparency and has improved brittleness (see Patent Document 3).

  As described above, it is required to provide a resin composition having fluidity and impact resistance comparable to a resin composition composed of an aromatic polycarbonate resin and an ABS resin, and having a good hue, and such a resin composition is There is a need for resin compositions that are useful for reducing environmental burdens. On the other hand, the various proposals relating to polylactic acid have not yet presented sufficient knowledge for solving the problem. Furthermore, none of the proposals give specific knowledge regarding the flame retardancy of polylactic acid-containing materials and their improvement, and the materials often exhibit high flame retardancy (for example, V-0 rank in UL standard 94). Conventional techniques have not been sufficient for application to required electrical and electronic equipment.

JP 7-506863 A JP-A-7-109413 JP-A-11-140292

  Therefore, the first object of the present invention is to have impact resistance and molding processability (fluidity) comparable to a resin composition (PC / ABS resin composition) of an aromatic polycarbonate resin and an ABS resin, and An object of the present invention is to provide a method for using an aromatic polycarbonate resin composition that is excellent in heat resistance and hue of a molded product with respect to the resin composition and in addition has a reduced environmental load as an exterior material for OA equipment or home appliances. . The second object of the present invention is to expand the application of deoiled resource materials by providing materials having high flame retardancy often required for materials for electric and electronic equipment while containing deoiled resource materials. In addition, the ratio of the petroleum-depleted resource material in the entire resin material is increased, thereby contributing to the reduction of the environmental burden. The third object of the present invention is to provide high flame retardancy, impact resistance and molding processability (fluidity) comparable to PC / ABS resin compositions, and heat resistance and molded products superior to the resin compositions. It is another object of the present invention to provide a method for using an aromatic polycarbonate resin composition having a hue of ## EQU2 ## and an environmental load-reducing material as an exterior material for OA equipment or home appliances.

  As a result of diligent research to achieve the above object, the present inventors have determined from a copolymer of aromatic polycarbonate and polylactic acid and / or lactic acid and other hydroxycarboxylic acid, and a specific ratio of core-shell type graft copolymer. It has been surprisingly found that the resulting composition has a good hue and excellent thermal stability, and a resin composition capable of achieving the first object is obtained. Furthermore, it discovered that the above-mentioned 2nd and 3rd objective can be achieved by combining a flame retardant (especially phosphate ester type flame retardant) of a specific ratio with respect to this composition. The present inventors have further studied based on such knowledge and completed the present invention.

The present invention comprises (1) (A) 100 parts by weight of an aromatic polycarbonate resin (component A),
(B) a copolymer of polylactic acid and / or lactic acid and other hydroxycarboxylic acid (component B) 5 to 80 parts by weight, and (C) a core of a rubber component having a glass transition temperature of 10 ° C. or less, a fragrance A core-shell type graft copolymer in which one or two or more shells of monomers selected from vinyl group vinyl, vinyl cyanide, acrylic acid ester, methacrylic acid ester, and vinyl compounds copolymerizable therewith are graft-copolymerized. Containing 3 to 50 parts by weight of polymer (component C),
And the composition ratio (B weight part) of B component per 100 weight part of A component, and the composition ratio (C weight part) of C component are in the range with which the following formula (I) is satisfy | filled (henceforth, This may be referred to as “Composition-I”) as an exterior material for OA equipment or home appliances.
0.4 × B ≦ C ≦ 1.2 × B (I)
According to this configuration (1), the above-mentioned problems have been solved, the impact resistance and molding processability (fluidity) comparable to those of the PC / ABS resin composition, and heat resistance to the resin composition. There is provided a method of using an aromatic polycarbonate resin composition having excellent properties and hue of a molded article and having a reduced environmental load as an exterior material for OA equipment or home appliances.

The present invention also includes (2) (A) 100 parts by weight of an aromatic polycarbonate resin (component A),
(B) 5-80 parts by weight of a copolymer (component B) of polylactic acid and / or lactic acid and other hydroxycarboxylic acid,
(C) One type of monomer selected from aromatic vinyl, vinyl cyanide, acrylic ester, methacrylic ester, and vinyl compounds copolymerizable therewith in the core of the rubber component having a glass transition temperature of 10 ° C. or lower Or 3 to 50 parts by weight of a core-shell type graft copolymer (component C) obtained by graft copolymerization of two or more shells, and (D) a flame retardant (component D) 0.05 to 50 parts by weight. ,
And the composition ratio (B weight part) of B component per 100 weight part of A component, and the composition ratio (C weight part) of C component are in the range with which the following formula (I) is satisfy | filled (henceforth, This may be referred to as “Composition-II”) as an exterior material for OA equipment or home appliances.
0.4 × B ≦ C ≦ 1.2 × B (I)
In a more preferred embodiment, (3) the composition ratio of B component (B part by weight) and the composition ratio of D component (D part by weight) per 100 parts by weight of component A are in a range satisfying the following formula (II). This is the method (2).
0.05 × B ≦ D ≦ 10 × B (II)
According to the configurations (2) and (3), the above-described problems are solved, and an aromatic polycarbonate resin composition having higher flame retardancy in addition to the characteristics of the composition-I described above is used as an OA device. Alternatively, a method for use in a packaging material for home appliances is provided.

One of the preferred embodiments of the present invention is that (4) the polycarbonate resin composition further contains 0.001 to 1 part by weight of (E) a phosphorus stabilizer (E component) per 100 parts by weight of the A component. This is the method of (1) to (3). According to this configuration (4), there is provided a method of using an aromatic polycarbonate resin composition that has further improved thermal stability and achieved a good hue as an exterior material for OA equipment or home appliances.
One of the preferred embodiments of the present invention is the method of (2) to (4) above, wherein (5) the component D is a compound containing no chlorine atom or bromine atom. A flame retardant composed of a compound containing a chlorine atom and a bromine atom may be considered unfavorable when performing incineration disposal or thermal recycling. In this respect, these flame retardants are somewhat poor in versatility. According to this configuration (5), there is provided a method of using an aromatic polycarbonate resin composition with reduced environmental burden and improved flame retardancy as an exterior material for OA equipment or home appliances.

  One of the more preferable embodiments is (6) the method of (2) to (5) above, wherein the component D is a phosphate ester flame retardant. According to this configuration (6), the aromatic polycarbonate resin composition having a further improved hue, reduced environmental load and improved flame retardancy is surprisingly used as an exterior material for OA equipment or home appliances. A method is provided.

  One of the preferred embodiments of the present invention is as follows. (7) The component A contains a recycled aromatic polycarbonate resin in an amount of 5% by weight or more in 100% by weight of the component A. This is the method (6). The effect of the present invention is also exerted satisfactorily when a recycled aromatic polycarbonate resin is included, in which the deterioration of the hue tends to become more prominent. Therefore, according to the configuration (7), the effect of the present invention is obtained. And the method of using the aromatic polycarbonate resin composition in which environmental burden was further reduced for the exterior material of OA equipment or household appliances is provided.

  In the present invention, the aromatic polycarbonate resin composition (Composition-I) is a resin composition containing an aromatic polycarbonate resin, polylactic acid and a core-shell type graft copolymer, and the aromatic polycarbonate resin and the ABS resin. Resin with impact resistance and molding processability (fluidity) comparable to that of the resin composition, excellent heat resistance and hue of the molded product, and reduced environmental impact Since the composition is a composition having good flame retardancy in addition to such properties, the composition-II is useful as an exterior material for OA equipment or home appliances, and has the industrial effects. Is exceptional.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic front perspective view of a molded product simulating a notebook personal computer housing used in Examples (length 178 mm × width 245 mm × edge height 10 mm, thickness 1.2 mm). It is the surface side front schematic diagram of the molded article used in the Example, and shows the gate position, the state of the weld line, and the cutout portion of the sample for evaluation. It is the back side front schematic diagram of the molded article used in the Example, and shows a mode that there is a boss with a rib (the part of a matte surface becomes a boss with a rib on both upper and lower sides).

  Hereinafter, each component which comprises the resin composition of this invention, those compounding ratios, a manufacturing method, etc. are demonstrated concretely one by one.

<About component A>
Component A in the aromatic polycarbonate resin composition of the present invention is an aromatic polycarbonate resin that is a main component of the resin composition. A typical aromatic polycarbonate resin (hereinafter sometimes simply referred to as “polycarbonate”) is obtained by reacting a dihydric phenol and a carbonate precursor, and as a reaction method, an interfacial polycondensation method, Examples thereof include a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  Specific examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as “bisphenol”). A ″), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4, 4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropylidene) Phenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4- Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5-dibromo- 4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Is mentioned. Among these, bis (4-hydroxyphenyl) alkane, especially bisphenol A (hereinafter sometimes abbreviated as “BPA”) is widely used.

In the present invention, in addition to bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, it is possible to use a special polycarbonate produced using other dihydric phenols as the A component.
For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the component A constituting the resin composition is a copolymerized polycarbonate of the following (1) to (3). is there.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Of 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Is 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis -Copolymer polycarbonate in which TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).

These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.
The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.
Of the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition and the like have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where form stability is required.
(I) polycarbonate having a water absorption of 0.05 to 0.15% by weight, preferably 0.06 to 0.13% by weight, and Tg of 120 to 180 ° C., or (ii) Tg of 160 to 250 ° C, preferably 170-230 ° C, and the water absorption is 0.10-0.30% by weight, preferably 0.13-0.30% by weight, more preferably 0.14-0.27% by weight. Some polycarbonate.
Here, the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

On the other hand, as the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples thereof include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.
In producing a polycarbonate from such a dihydric phenol and a carbonate precursor by an interfacial polymerization method, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The polycarbonate may be a branched polycarbonate copolymerized with a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound used here include 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxy). Phenyl) ethane and the like.
When the polyfunctional compound which produces a branched polycarbonate is included, the ratio is 0.001-1 mol% in the total amount of polycarbonate, preferably 0.005-0.9 mol%, particularly preferably 0.01-0.8. Mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0.9% in the total amount of the polycarbonate. Those having a mol%, particularly preferably 0.01 to 0.8 mol% are preferred. The ratio of the branched structure can be calculated by ¹ H-NMR measurement.

In addition, the aromatic polycarbonate resin as the component A in the resin composition of the present invention is a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, a bifunctional alcohol (fatty acid). It may be a copolymerized polycarbonate copolymerized with a cyclic group) and a polyester carbonate copolymerized with such a bifunctional carboxylic acid and a bifunctional alcohol. Moreover, the mixture which blended 2 or more types of the obtained polycarbonate may be used.
The aliphatic bifunctional carboxylic acid used here is preferably an α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include, for example, sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and the like, and saturated aliphatic dicarboxylic acid and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.

Furthermore, in the present invention, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can be used as the component A.
The aromatic polycarbonate resin as component A is a mixture of two or more of polycarbonates such as polycarbonates having different dihydric phenols, polycarbonates containing branched components, polyester carbonates, and polycarbonate-polyorganosiloxane copolymers. There may be. Furthermore, what mixed 2 or more types of polycarbonates from which a manufacturing method differs, a polycarbonate from which a terminal stopper differs, etc. can also be used.
In the polymerization reaction of polycarbonate, the reaction by the interfacial polycondensation method is usually a reaction of 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. In order to accelerate the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound can be used. . At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

In such a polymerization reaction, a terminal terminator is usually used. Monofunctional phenols can be used as such end terminators. As monofunctional phenols, for example, monofunctional phenols such as phenol, p-tert-butylphenol, and p-cumylphenol are preferably used. Furthermore, as monofunctional phenols, long chain alkyl groups having 10 or more carbon atoms such as decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol are used. A monofunctional phenol substituted with a nucleus can be mentioned, and the phenol is effective in improving fluidity and hydrolysis resistance. Such end terminators 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. The dihydric phenol and the carbonate ester are mixed with heating in the presence of an inert gas to produce an alcohol or It is carried out by a method of distilling phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but in most cases is in the range of 120 to 350 ° C. In the latter stage of the reaction, the reaction system is evacuated to about 1.33 × 10 ^{3 to} 13.3 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.
Examples of the carbonate ester include esters such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Among them, diphenyl carbonate is preferable.

A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt and potassium salt of dihydric phenol; alkaline earth metal compounds such as calcium hydroxide, barium hydroxide and magnesium hydroxide; Nitrogen-containing basic compounds such as methylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, and triethylamine can be used. Furthermore, alkoxides of alkali (earth) metals, organic acid salts of alkali (earth) metals, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds, etc., esterification reaction, transesterification The catalyst used for the reaction can be used. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is preferably selected in the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻³ equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents, relative to 1 mol of dihydric phenol as a raw material. It is.
In the reaction by the melt transesterification method, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate, 2-ethoxycarbonyl is used at the later stage or after completion of the polycondensation reaction for the purpose of reducing the phenolic end groups of the produced polycarbonate. Compounds such as phenylphenyl carbonate can be added.

Furthermore, in the melt transesterification method, it is preferable to use a deactivator that neutralizes the activity of the catalyst. The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst. Moreover, it is suitable to use in the ratio of 0.01-500 ppm with respect to the polycarbonate after superposition | polymerization, More preferably, it is 0.01-300 ppm, Most preferably, it is a ratio of 0.01-100 ppm. Examples of preferable quenching agents include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.
The viscosity average molecular weight of the aromatic polycarbonate resin to be the component A is not limited. However, when the viscosity average molecular weight is less than 10,000, the strength and the like are lowered, and when it exceeds 50,000, the molding process characteristics are lowered. Therefore, the range of 10,000 to 50,000 is preferable. The range of 3,000 to 30,000 is more preferable, and the range of 14,000 to 28,000 is more preferable. In this case, it is also possible to mix a polycarbonate having a viscosity average molecular weight outside the above range within a range in which moldability and the like are maintained. For example, a high molecular weight polycarbonate component having a viscosity average molecular weight exceeding 50,000 can be blended.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of aromatic polycarbonate in 100 ml of methylene chloride at 20 ° C. with a specific viscosity (η _SP ) calculated by the following formula. ,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7
In addition, when measuring the viscosity average molecular weight in the resin composition of this invention, it carries out in the following way. That is, the resin composition is dissolved in 20 to 30 times its weight of methylene chloride, and the soluble component is collected by Celite filtration, and then the solution is removed and dried sufficiently to obtain a solid component soluble in methylene chloride. . A specific viscosity (η _SP ) at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride using an Ostwald viscometer, and the viscosity average molecular weight M is calculated by the above formula.

  The aromatic polycarbonate resin which is the component A of the present invention can be reused. In that case, the proportion of components having a small environmental load increases together with the B component of the non-petroleum resource material, which is a more preferable material in terms of the environmental load reduction effect. The recycled aromatic polycarbonate resin means a resin recovered without obtaining a polymer decomposition step from a resin molded product formed by at least a processing step for producing a target product. For example, a used product Typical examples are resin molded products that are separated and collected from plastic, resin molded products that are separated and collected from defective products during product manufacturing, and resin molded products that include unnecessary parts such as spools and runners that occur during molding. Is done. The decomposition step refers to a step aimed at decomposing the bonds forming the main chain of the aromatic polycarbonate and recovering the monomers and oligomers produced by the decomposition, and is intended for kneading, pulverization, processing, etc. It does not mean thermal decomposition in the process. On the other hand, the so-called virgin aromatic polycarbonate resin is usually a resin produced in-house as well as a resin obtained from the market, and its form is powdered, pelletized, chip-shaped or spherically granulated. Usually used. The reused aromatic polycarbonate resin preferably contains 90% by weight or more of the aromatic polycarbonate component in 100% by weight of the resin material, more preferably 95% by weight or more, and still more preferably 98% by weight. What is contained above is used.

  The used products include soundproof walls, glass windows, translucent roofing materials, various glazing materials represented by automobile sunroofs, transparent members such as windshields and automobile headlamp lenses, containers such as water bottles, and light. A recording medium is preferred. These do not contain a large amount of additives or other resins, and the desired quality is easily obtained stably. In particular, a preferable example is a molded product in which a hard coat film is laminated on the surface of a transparent polycarbonate resin molded product. This is because such molded articles are often colored by the influence of the hard coat agent while having good transparency. Specific examples of such molded articles include various glazing materials, transparent members such as windshields and automobile headlamp lenses.

  Moreover, the recycled aromatic polycarbonate resin can use either the pulverized product of the resin molded product which has become unnecessary or pellets produced by remelting and extruding the pulverized product. In addition, if the resin molded product has a printed coating film, seal, label, decorative coating film, conductive coating, conductive plating, metal deposition, etc., the pulverized product from which such portions have been removed (after pulverization and pulverization after removal) Any of the pellets produced by remelting and extruding the pulverized product can be used. When the printed coating film is included, the effect of the present invention is not sufficiently exhibited because it is easy to be colored due to these influences. Therefore, it is preferable in the present invention to remove the printed coating film. As a method of removing such a printed coating film or plating, a method of rolling between two rolls, a method of contacting with heated / pressurized water, various solvents, an acid / alkaline aqueous solution, or the like, a method of mechanically scraping off the removed portion , A method of irradiating ultrasonic waves, a method of blasting, and the like, and a combination of these can also be used.

On the other hand, in a molded product in which a hard coat film is laminated on the surface of a transparent polycarbonate resin molded product, it is possible to achieve a good hue, so it is more efficient to blend the pulverized product as it is, and environmental impact Contributes to the reduction of The pulverized product can be produced by pulverizing a resin molded product using a known pulverizer.
The recycled aromatic polycarbonate resin can be contained in 100% by weight of the A component aromatic polycarbonate resin, preferably 5% by weight or more, more preferably 10% by weight or more, and further preferably 15% by weight or more. The upper limit can be 100% by weight, but practically it is preferably 50% by weight or less because a resin composition with more stable characteristics can be obtained.

<About B component>
Among the copolymers of polylactic acid and / or lactic acids and other hydroxycarboxylic acids which are the B component of the present invention, polylactic acid is synthesized by ring-opening polymerization from a cyclic dimer of lactic acid, usually called lactide, The manufacturing method is disclosed in USP 1,995,970, USP 2,362,511, USP 2,683,136. Copolymers of lactic acid and other hydroxycarboxylic acids are usually synthesized by ring-opening polymerization from a cyclic ester intermediate of lactide and hydroxycarboxylic acid, and their production methods are disclosed in USP 3,635,956 and USP 3,797,499. Has been. In the case of producing a lactic acid resin by direct dehydration polycondensation without using ring-opening polymerization, lactic acids and other hydroxycarboxylic acids as necessary are preferably azeotroped in the presence of an organic solvent, particularly a phenyl ether solvent. A lactic acid resin having a degree of polymerization suitable for the present invention is obtained by polymerizing by a method of dehydrating condensation and, particularly preferably, removing water from a solvent distilled by azeotropic distillation to return it to a substantially anhydrous solvent. Is obtained. L- and D-lactic acid, a mixture thereof, or lactide, which is a dimer of lactic acid, can be used as the starting lactic acid. Other hydroxycarboxylic acids that can be used in combination with lactic acids include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, and 6-hydroxycaproic acid. A cyclic ester intermediate of carboxylic acid, for example, glycolide, which is a dimer of glycolic acid, or ε-caprolactone, which is a cyclic ester of 6-hydroxycaproic acid, can also be used. In the production of the lactic acid-based resin, an appropriate molecular weight regulator, branching agent, other modifier, etc. may be added. In addition, lactic acids and hydroxycarboxylic acids as copolymer components can be used alone or in combination of two or more, and two or more of the obtained lactic acid resins can be used in combination. In the present invention, polylactic acid, which is a polymer containing only lactic acids, is preferably used, and poly L-lactic acid resin containing L-lactic acid as a main raw material is particularly preferable. Although the compounding quantity of B component is 1-100 weight part per 100 weight part of A component, 5-80 weight part is preferable and 10-30 weight part is more preferable. When the blending amount is less than 1 part by weight, improvement in fluidity and rigidity is not observed, and when it exceeds 100 parts by weight, the heat resistance is remarkably lowered, which is not preferable.

<About component C>
An elastic polymer can be used as the impact modifier as the component C of the present invention. Examples of the elastic polymer include rubber components having a glass transition temperature of 10 ° C. or lower, aromatic vinyl, vinyl cyanide, Mention may be made of graft copolymers in which one or more monomers selected from acrylic esters, methacrylic esters and vinyl compounds copolymerizable therewith are copolymerized. A more preferable elastic polymer is a core-shell type graft copolymer in which one or more shells of the above-mentioned monomer are graft-copolymerized on the core of the rubber component.
Moreover, the rubber component and the block copolymer of the said monomer are also mentioned. Specific examples of such block copolymers include thermoplastic elastomers such as styrene / ethylenepropylene / styrene elastomers (hydrogenated styrene / isoprene / styrene elastomers) and hydrogenated styrene / butadiene / styrene elastomers. Furthermore, various elastic polymers known as other thermoplastic elastomers such as polyurethane elastomers, polyester elastomers, polyether amide elastomers and the like can also be used.

A core-shell type graft copolymer is more preferable as the component C of the present invention. In the core-shell type graft copolymer, the core particle size is preferably 0.05 to 0.8 μm, more preferably 0.1 to 0.6 μm, and more preferably 0.1 to 0.5 μm in weight average particle size. Is more preferable. If it is in the range of 0.05 to 0.8 μm, better impact resistance is achieved. The elastic polymer preferably contains 40% or more of a rubber component, and more preferably contains 60% or more.
As the rubber component of component C, butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicone composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, nitrile rubber , Ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to these unsaturated bonds, but in view of concerns about the generation of harmful substances during combustion, halogen A rubber component containing no atoms is preferable in terms of environmental load.

  The glass transition temperature of the rubber component is preferably −10 ° C. or lower, more preferably −30 ° C. or lower. As the rubber component, butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, and acrylic-silicone composite rubber are particularly preferable. The composite rubber is a rubber obtained by copolymerizing two kinds of rubber components or a rubber polymerized so as to have an IPN structure entangled with each other so as not to be separated. If a rubber component having a refractive index difference from the aromatic polycarbonate resin of greater than 0.015 is used, the pearly luster of the composition will be reduced. do it. The difference in refractive index from the aromatic polycarbonate resin of the rubber component is more preferably larger than 0.020. In this respect, the refractive index of the rubber component is more specifically preferably in the range of 1.48 to 1.56, and more preferably in the range of 1.50 to 1.54.

A butadiene rubber is more preferable as the rubber component of the core-shell type graft copolymer suitable for the component C of the present invention. This is because the rubber component is relatively susceptible to hue deterioration due to heat load, and the effects of the present invention are more effectively exhibited, as well as a molded product having a more uniform appearance that satisfies the above-mentioned refractive index conditions. It is easy to obtain.
Examples of the aromatic vinyl in the vinyl compound copolymerized with the rubber component include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, halogenated styrene and the like, and styrene is particularly preferable. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate, and the like. Examples of the methacrylate ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate. , Cyclohexyl methacrylate, octyl methacrylate and the like, and methyl methacrylate is particularly preferable. Among these, it is particularly preferable to contain a methacrylic ester such as methyl methacrylate as an essential component. Since this is excellent in affinity with the aromatic polycarbonate resin, more elastic polymers are present in the resin, and the good impact resistance of the aromatic polycarbonate resin is more effectively exhibited. As a result, the impact resistance of the resin composition is improved. More specifically, the methacrylic acid ester is contained in 100% by weight of the graft component (in the case of 100% by weight of the shell in the case of the core-shell type polymer), preferably 10% by weight or more, more preferably 15% by weight or more. Is done.

  The elastic polymer containing a rubber component having a glass transition temperature of 10 ° C. or less may be produced by any polymerization method including bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. It can be a single-stage graft or a multi-stage graft. Moreover, the mixture with the copolymer of only the graft component byproduced in the case of manufacture may be sufficient. Furthermore, examples of the polymerization method include a general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, and a two-stage swelling polymerization method. In the suspension polymerization method, the aqueous phase and the monomer phase are individually maintained, both are accurately supplied to the continuous disperser, and the particle diameter is controlled by the rotation speed of the disperser, and the continuous production is performed. In the method, a method may be used in which the monomer phase is supplied by passing it through a fine orifice having a diameter of several to several tens of μm or a porous filter in an aqueous liquid having dispersibility to control the particle size. In the case of a core-shell type graft polymer, the reaction may be one stage or multistage for both the core and the shell.

  Such polymers are commercially available and can be easily obtained. For example, as rubber components mainly composed of butadiene rubber, acrylic rubber or butadiene-acrylic composite rubber, Kane Ace B series (for example, B-56 etc.) of Kanegafuchi Chemical Industry Co., Ltd. and Metabrene of Mitsubishi Rayon Co., Ltd. C series (for example, C-223A), W series (for example, W-450A), paraloid EXL series (for example, EXL-2602) by Kureha Chemical Industry, HIA series (for example, HIA-15), BTA series (E.g., BTA-III), KCA series, Rohm and Haas Paraloid EXL series, KM series (e.g., KM-336P, KM-357P, etc.), Ube Sycon Corporation UCL modifier resin series (UMG) UMG's UMG AXS resin series), and those mainly composed of acrylic-silicone composite rubber as the rubber component include those commercially available from Mitsubishi Rayon Co., Ltd. under the trade name of Methbrene S-2001 or SRK-200.

  The composition ratio of component C is 0.2 to 100 parts by weight per 100 parts by weight of component A, but preferably 1.5 to 80 parts by weight, more preferably 3 to 50 parts by weight. When the composition ratio is less than 0.2 parts by weight, the reinforcing effect on the mechanical properties such as impact resistance of the resin composition of the present invention is not sufficient, and when it exceeds 100 parts by weight, molding processability and hue Is not preferable because it deteriorates.

Furthermore, the composition ratio of the B and C components of the present invention must satisfy the following formula (I).
0.2 × B ≦ C ≦ 2 × B (I)
The left side (lower limit of C) of the above formula (I) is preferably 0.3 × B, more preferably 0.4 × B, and the right side (upper limit of C) is preferably 1.5 × B. More preferably, it is 1.2 × B. In the range of the above formula (I), a good hue can be achieved, and a more uniform appearance can be achieved.

<About D component>
Examples of the flame retardant for component D used in the composition-II in the present invention include halogenated flame retardants such as brominated epoxy resins, brominated polystyrenes, brominated polycarbonates, brominated polyacrylates, and chlorinated polyethylenes, and monophosphates. Phosphoric ester flame retardants such as compounds and phosphate oligomer compounds, organic phosphorus flame retardants other than phosphate ester flame retardants such as phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds, organic sulfonate alkalis (earths) ) Metal salt, metal borate flame retardant, organo metal salt flame retardant such as metal stannate flame retardant, and silicone flame retardant. Separately, a flame retardant aid (for example, sodium antimonate, antimony trioxide, etc.), an anti-drip agent (polytetrafluoroethylene having fibril-forming ability, etc.), etc. may be blended and used together with the flame retardant. With these blends, flame retardancy is imparted to the resin composition, and the resin composition is suitable for the electric / electronic field, OA field, home appliance field, and the like.

Among the above-mentioned flame retardants, compounds that do not contain chlorine and bromine atoms have reduced features that are undesirable when performing incineration and thermal recycling. It is more suitable as a flame retardant in the resin composition of the present invention.
Furthermore, the phosphoric ester-based flame retardant is the most suitable flame retardant because the good hue intended by the present invention is further improved. In addition, the phosphate ester flame retardant also exhibits the effect of improving the molding processability. Specific examples of the phosphate ester flame retardant include one or more phosphate ester compounds represented by the following general formula (i).

(However, X in the above formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis A group derived from (4-hydroxyphenyl) sulfide, and n is an integer of 0 to 5, or an average value of 0 to 5 in the case of a mixture of phosphate esters having different numbers of n, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently a group derived from phenol, cresol, xylenol, isopropylphenol, butylphenol, p-cumylphenol substituted or unsubstituted with one or more halogen atoms. .)
More preferable examples include groups in which X in the above formula is derived from hydroquinone, resorcinol, bisphenol A, and dihydroxydiphenyl, and n is an integer of 1 to 3, or a different number of phosphate esters. In the case of blends of R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ each independently of one or more halogen atoms substituted or more preferably substituted phenol, cresol, A group derived from xylenol.

  Among such organophosphate flame retardants, triphenyl phosphate is preferable as a phosphate compound, and resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are preferable as phosphate oligomers because of excellent hydrolysis resistance. Can be used. More preferable are resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) from the viewpoint of heat resistance. This is because they have good heat resistance and are free from adverse effects such as thermal deterioration and volatilization.

In composition-II, the flame retardant of component D is contained in the range of 0.05 to 50 parts by weight per 100 parts by weight of component A. If it is less than 0.05 part by weight, sufficient flame retardancy is not exhibited, and if it exceeds 50 parts by weight, the strength and heat resistance of Composition-II are impaired. A more preferable ratio of component D is such that the composition ratio of component B (B part by weight) and the composition ratio of component D (D part by weight) per 100 parts by weight of component A satisfy the following formula (II).
0.05 × B ≦ D ≦ 10 × B (II)
The left side (lower limit of D) of the above formula (II) is preferably 0.5 × B, more preferably 0.7 × B, and the right side (upper limit of D) is preferably 3 × B. Preferably 2 × B. In the range of the above formula (II), it is possible to achieve both high flame retardancy often required in materials for electric / electronic devices and various properties exhibited in Composition-I. Examples of such high flame retardancy include achieving V-0 rank in UL standard 94 at a thickness of 1.6 mm.

<About E component>
In the present invention, in order to obtain an aromatic polycarbonate resin composition having a better hue and stable fluidity, it is preferable to contain a phosphorus stabilizer as the E component. In particular, a pentaerythritol type phosphite compound represented by the following general formula (ii) is preferably blended as a phosphorus stabilizer.

[Wherein R ¹ and R ² are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkylaryl group, an aralkyl group having 7 to 30 carbon atoms, and an alkyl group having 4 to 20 carbon atoms. A cycloalkyl group, a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms is shown. In addition, the cycloalkyl group and the aryl group may be substituted with an alkyl group. ]
More specifically, examples of the pentaerythritol type phosphite compound include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, and the like are preferable. Among them, distearyl pentaerythritol diphosphite and bis (2,4-di-te) are preferable. Include t- butylphenyl) pentaerythritol diphosphite.
Examples of other phosphorus stabilizers include various other phosphite compounds, phosphonite compounds, and phosphate compounds.

  Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris (diethylphenyl) phos Phyto, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite Ito, and tris (2,6-di -tert- butylphenyl) phosphite and the like.

  Still other phosphite compounds that react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

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

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
Said phosphorus stabilizer can be used individually or in combination of 2 or more types, It is preferable to mix | blend an effective amount of a pentaerythritol type | mold phosphite compound at least. The phosphorus stabilizer is preferably blended in an amount of 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and still more preferably 0.01 to 0.3 part by weight per 100 parts by weight of component A. .

  In the present invention, various generally known reinforcing fillers such as glass fiber, carbon fiber, glass flake, wollastonite, kaolin clay, mica, and talc can be used in combination according to the purpose of use. Glass fibers, carbon fibers, glass flakes, and the like are suitable for improving the strength (such as tensile strength and bending strength) and rigidity (such as bending elastic modulus) of the resin composition. On the other hand, in the case of effectively utilizing the impact resistance characteristic of the composition of the present invention, the composition contains a small amount of a fine reinforcing filler such as talc and wollastonite (25 parts by weight or less per 100 parts by weight of component A). It is particularly preferred. The shape of the filler can be freely selected from fibrous, flake, spherical and hollow. The reinforcing filler is preferably 100 parts by weight or less, more preferably 1 to 50 parts by weight, and still more preferably 5 to 25 parts by weight per 100 parts by weight of the component A.

  Moreover, this invention can contain the folding inhibitor for suppressing the folding of the said filler. The breakage suppressor inhibits adhesion between the matrix resin and the reinforcing filler, reduces stress acting on the reinforcing filler during melt kneading, and suppresses breakage of the reinforcing filler. Specifically, the crease suppressor has (i) a compound having a low affinity with the resin, and (ii) a compound having a low affinity with the resin when the compound having a low affinity with the resin is directly coated on the surface of the reinforcing filler. It is a compound having a functional group capable of reacting with the surface of the filler.

One suitable folding inhibitor is an alkoxysilane compound in which an alkyl group having 5 or more carbon atoms is bonded to a silicon atom. The number of carbon atoms of the alkyl group bonded to the silicon atom is preferably 5 to 60, more preferably 5 to 20, still more preferably 6 to 18, and particularly preferably 8 to 16. The alkyl group is preferably 1 or 2, particularly preferably 1. Further, preferred examples of the alkoxy group include a methoxy group and an ethoxy group. Such alkoxysilane compounds are preferable in that they have high reactivity with the reinforcing filler surface and excellent coating efficiency. Therefore, it is suitable for a finer reinforcing filler.
One suitable folding inhibitor is a polyolefin wax having at least one functional group selected from a carboxyl group and a carboxylic anhydride group. The molecular weight is preferably 500 to 20,000, more preferably 1,000 to 15,000 in terms of weight average molecular weight. In such a polyolefin wax, the amount of carboxyl group and carboxylic anhydride group is in the range of 0.05 to 10 meq / g per gram of lubricant having at least one functional group selected from carboxyl group and carboxylic anhydride group. Is preferable, more preferably 0.1 to 6 meq / g, and still more preferably 0.5 to 4 meq / g. It is preferable that the ratio of the functional group in the folding inhibitor is the same as the ratio of the carboxyl group and the carboxylic anhydride group in the functional group other than the carboxyl group.
The folding inhibitor is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight, and still more preferably 0.1 to 0.8 parts by weight per 100 parts by weight of component A.

  Furthermore, in the present invention, the aromatic polycarbonate resin composition includes other thermoplastic resins (for example, polyalkylene terephthalate resin, polyarylate resin, liquid crystalline polyester resin, polyamide resin, polyimide, and the like within the range in which the effects of the present invention are exhibited. Resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resin such as polyethylene and polypropylene, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / Styrene copolymer (ABS resin), polystyrene resin, high impact polystyrene resin, syndiotactic polystyrene resin, polymethacrylate resin, and phenoxy Epoxy resin, etc.), nucleating agents (eg, sodium stearate, ethylene-sodium acrylate, etc.), antioxidants (eg, hindered phenolic compounds, sulfur-based antioxidants, etc.), UV absorbers (benzoic acid) Triazole, triazine, benzophenone, etc.), light stabilizer (HALS, etc.), mold release agent (saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax, fluorine compound, paraffin wax, beeswax, etc.), flow modifier (Polycaprolactone, etc.), colorants (carbon black, titanium dioxide, various organic dyes, metallic pigments, etc.), light diffusing agents (acrylic crosslinked particles, silicone crosslinked particles, etc.), fluorescent brighteners, phosphorescent pigments, fluorescent dyes , Antistatic agent, inorganic and organic antibacterial agent, photocatalytic antifouling agent (fine particle titanium oxide, fine particle Such as children zinc oxide), the infrared absorbing agent, and may be blended and photochromic agent ultraviolet absorber. These various additives can be used in known blending amounts when blended with the aromatic polycarbonate resin.

  Arbitrary methods are employ | adopted in order to manufacture the resin composition of this invention. For example, each component and optionally other components can be premixed and then melt-kneaded and pelletized. Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. In the preliminary mixing, granulation can be performed by an extrusion granulator or a briquetting machine depending on the case. After the preliminary mixing, the mixture is melt-kneaded by a melt-kneader represented by a vent type twin-screw extruder and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant temperature stirring vessel, but a vent type twin screw extruder is preferred. In addition, each component and optionally other components can be independently supplied to a melt-kneader represented by a twin-screw extruder without being premixed.

  In addition, when the pulverized material of a molded product is mix | blended as A component, this pulverized material has a comparatively high characteristic. Therefore, in the supply of the extruder, it is preferable to mix with other components having a high bulk density, or to supply to the extruder together with the components having a high bulk density even when they are supplied independently. The deterioration of the resin caused by the aromatic polycarbonate resin reused by such a production method is further suppressed, and a resin composition part having a more suitable hue can be obtained. The liquid raw material is preferably supplied independently using a separate liquid injection device. Further, when a reinforcing filler is included, the filler can be supplied from the first supply port at the root of the extruder screw, but supply by a side feeder from the second supply port in the middle of the extruder is more preferable.

  In the present invention, the aromatic polycarbonate resin composition can be produced in various products by usually injection-molding the pellets produced by the above-described method to obtain molded products. In such injection molding, not only a normal cold runner molding method but also a hot runner molding method is possible. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known.

  In the present invention, the aromatic polycarbonate resin composition can also be used in the form of various shaped extruded products, sheets, films and the like by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the aromatic polycarbonate resin composition of the present invention can be made into a hollow molded product by rotational molding or blow molding.

  In the present invention, the polycarbonate resin composition is suitable, for example, as an exterior material for office automation equipment and home appliances. For example, personal computers, notebook computers, game machines (home game machines, arcade game machines, pachinko machines, slot machines, etc.) , Display devices (CRT, liquid crystal, plasma, projector, organic EL, etc.), mice, and exterior materials such as printers, copiers, scanners and fax machines (including these multifunction devices), keyboard keys and various switches A switch molded product is exemplified. Furthermore, the aromatic polycarbonate resin composition of the present invention is useful for a wide variety of other applications, such as portable information terminals (so-called PDAs), cellular phones, portable books (dictionaries, etc.), portable televisions, recording media (CD, MD). , DVD, next-generation high-density disk, hard disk, etc.) drive, recording medium (IC card, smart media, memory stick, etc.) reader, optical camera, digital camera, parabolic antenna, electric tool, VTR, iron, hair dryer, Examples include rice cookers, microwave ovens, audio equipment, lighting equipment, refrigerators, air conditioners, air cleaners, negative ion generators, and typewriters, and various parts such as exterior materials of the present invention. Use resin products formed from aromatic polycarbonate resin compositions It is possible. Moreover, it is suitable for various miscellaneous goods such as various containers, covers, writing instrument bodies, and ornaments. Further examples include vehicle parts such as lamp sockets, lamp reflectors, lamp housings, instrument panels, center console panels, deflector parts, car navigation parts, car audio visual parts, and auto mobile computer parts.

  Furthermore, the resin molded product formed from the aromatic polycarbonate resin composition can be imparted with other functions by surface modification. Surface modification here means a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. The method used for normal resin molded products can be applied. The resin composition of the present invention can provide a good product with one coat even if the coating composition has a low hue due to its good hue.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these. In addition, the measurement of the various characteristics in an Example was based on the following method. The following raw materials were used as raw materials.

(1) Flexural modulus: The flexural modulus was measured according to ISO178. Test piece shape: length 80 mm × width 10 mm × thickness 4 mm.
(2) Charpy impact strength: Notched Charpy impact strength was measured in accordance with ISO179. Test specimen thickness 4 mm.
(3) Heat resistance: The deflection temperature under load was measured according to ISO75-1 and 2. Load: 1.80 MPa.
(4) Surface appearance: A case molded with a notebook personal computer as shown in FIG. 1 is observed, and the surface of the molded product is visually observed. When the pearly luster exhibits an extremely uneven color tone, ×, when a uniform color tone is exhibited. It was.
(5) Hue: Using a color computer (TC-1800MK-II: manufactured by Tokyo Denshoku Co., Ltd.), the L value and b value of the mirror surface portion of the casing molded product of the notebook computer shown in FIG. 1 were measured. .
(6) Fluidity: Archimedes spiral length of 1 mm flow path thickness and 8 mm flow path width with injection molding machine (Sumitomo Heavy Industries, Ltd. SG-150U), cylinder temperature 280 ° C, mold temperature 70 ° C, injection pressure It was measured at 98.1 MPa.
(7) Flammability: Flame retardancy at a test piece thickness of 1.6 mm was evaluated by a method (UL94) defined by US Underwriters Laboratories (evaluated only for those containing a phosphate ester flame retardant).
The following were used as raw materials.

(A component)
PC-1: Polycarbonate resin powder (manufactured by Teijin Chemicals Ltd .: Panlite L-1250WP, viscosity average molecular weight 23,900)
PC-2: Polycarbonate resin molded product pulverized product (polycarbonate resin pellets (manufactured by Teijin Chemicals Ltd .: Panlite L-1250, viscosity average molecular weight 23,700) was dried at 120 ° C. for 5 hours with a hot air circulation dryer, Collect the spool and runner part when molding the molded product for bending properties with an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) at a cylinder temperature of 290 ° C, a mold temperature of 80 ° C, and a molding cycle of 40 seconds. Crushing using a crusher (SB-210, manufactured by Horai Iron Works Co., Ltd.) equipped with a metal screen having many small holes of 8 mm, and crushing with a V-type blender. object)
(B component)
PLA: Polylactic acid (Mitsui Chemicals, Inc .: LACEA H-100J)
(C component)
C-1: Core-shell type elastic polymer (manufactured by Kureha Chemical Co., Ltd .: Paraloid EXL-2602, core-shell having 80% by weight of butadiene, 16% by weight of methyl methacrylate and 4% by weight of ethyl acrylate Type elastic polymer)
C-2: Core-shell type elastic polymer (manufactured by Mitsubishi Rayon Co., Ltd .: metabrene C-223A, core-shell type elastic polymer whose core is 70% by weight of butadiene and whose shell is styrene and methyl methacrylate)
(D component)
D-1: Phosphate ester flame retardant (Asahi Denka Kogyo Co., Ltd .: ADK STAB FP-500)
(E component)
E-1: Distearyl pentaerythritol diphosphite (Asahi Denka Kogyo Co., Ltd .: ADK STAB PEP-8)
(Other)
PTFE: Polytetrafluoroethylene having a fibril forming ability (manufactured by Daikin Industries, Ltd .: Polyflon MPA FA-500)
ABS: ABS resin pellets manufactured by the continuous bulk polymerization method (Mitsui Toatsu method) [manufactured by Nippon A & L Co., Ltd .: Santac UT-61]

[Examples 1-6, Comparative Examples 1-6]
A vented twin screw extruder having a diameter of 30 mmφ with an aromatic polycarbonate resin, polylactic acid, impact modifier, phosphorus stabilizer, and phosphate ester flame retardant having the composition shown in Tables 1 and 2 [Corporation] Nippon Steel Works TEX30XSST] was melt-extruded and pelletized at a cylinder temperature of 260 ° C., a screw speed of 150 rpm, a discharge rate of 20 kg / h, and a vent vacuum of 3 kPa.
The screw configuration is the first kneading zone (consisting of feed kneading disk x 2, feed rotor x 1, return rotor x 1 and return kneading disk x 1) before the side feeder position. A second-stage kneading zone (consisting of a feed rotor × 1 and a return rotor × 1) was provided after the feeder position.
In each Example and Comparative Example, all the components were uniformly mixed using a tumbler to prepare a premix, and the mixture was supplied from the first supply port of the extruder. In addition, PTFE was uniformly mixed in advance at a concentration of 2.5% by weight in PC-1, and the mixture was supplied to a tumbler.

  The obtained pellets were dried at 100 ° C. for 5 hours (a sample containing the E-1 component was 7 hours at 85 ° C.) with a hot air circulation dryer. After drying, a test for evaluating a bending elastic modulus, a deflection temperature under load, and a flammability in an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) with a cylinder temperature of 260 ° C., a mold temperature of 70 ° C., and a molding cycle of 40 seconds. A piece was molded. Also, the pellets after drying were used for an injection molding machine (ULTRA220-NIVA manufactured by Sumitomo Heavy Industries, Ltd.) with a cylinder inner diameter of 50 mmφ. Molding was performed at 80 ° C. (60 ° C. for the sample containing the D-1 component) at an injection speed of 75 mm / sec. Each characteristic was measured using these molded articles. The spiral flow length was measured by the above method. The results are shown in Tables 1 and 2.

  As is clear from the results of Tables 1 and 2, the resin composition containing polylactic acid has a clear improvement in L value and suppression of b value compared to the resin composition not containing polylactic acid, and is more easily colored. It turns out that it is a proper resin composition. Further, the resin composition of the present invention has a uniform appearance in which pearl luster has disappeared, and in addition, becomes a composition excellent in rigidity, heat resistance, and fluidity. Thus, it can be seen that the resin composition of the present invention is a resin composition having a property comparable to that of an ABS resin and an excellent hue with respect to an aromatic polycarbonate resin (the ABS resin used in the comparative example is a so-called This is an ABS resin manufactured by the continuous bulk polymerization method of Mitsui Toatsu, and it is an ABS resin that can produce a good hue with very little impurities without using any emulsifier or coagulant. The effect of improving the hue is further improved by the phosphorus-based stabilizer, and is clearer when a recycled aromatic polycarbonate resin is used. In addition, it can be seen that a composition having both a good hue and flame retardancy can be obtained by blending a phosphate ester flame retardant. Even in a resin composition containing a flame retardant, characteristics that cannot be achieved by combining an aromatic polycarbonate, an ABS resin, and an impact modifier can be obtained.

1 Molded product body imitating the housing of a notebook PC 2 Matte surface part 3 Mirror surface part 4 Gate (pin gate 0.8mmφ, 5 locations)
5 Approximate weld line 6 Cutout part 7 for evaluation sample Rib boss (corresponding to the back side of the mirror part)
8 Ribbed boss (corresponding to the back side of the mirror surface)

Claims (7)

(A) 100 parts by weight of an aromatic polycarbonate resin (component A),
(B) a copolymer of polylactic acid and / or lactic acid and other hydroxycarboxylic acid (component B) 5 to 80 parts by weight, and (C) a core of a rubber component having a glass transition temperature of 10 ° C. or less, a fragrance A core-shell type graft copolymer in which one or two or more shells of monomers selected from vinyl group vinyl, vinyl cyanide, acrylic acid ester, methacrylic acid ester, and vinyl compounds copolymerizable therewith are graft-copolymerized. Containing 3 to 50 parts by weight of polymer (component C),
In addition, an aromatic polycarbonate resin composition in which the composition ratio of B component (B parts by weight) and the composition ratio of C component (C parts by weight) per 100 parts by weight of component A satisfy the following formula (I) is used as OA equipment. Or the method used for the exterior material of household appliances.
0.4 × B ≦ C ≦ 1.2 × B (I) (A) 100 parts by weight of an aromatic polycarbonate resin (component A),
(B) 5-80 parts by weight of a copolymer (component B) of polylactic acid and / or lactic acid and other hydroxycarboxylic acid,
(C) One type of monomer selected from aromatic vinyl, vinyl cyanide, acrylic ester, methacrylic ester, and vinyl compounds copolymerizable therewith in the core of the rubber component having a glass transition temperature of 10 ° C. or lower Or 3 to 50 parts by weight of a core-shell type graft copolymer (component C) obtained by graft copolymerization of two or more shells, and (D) a flame retardant (component D) 0.05 to 50 parts by weight. ,
In addition, an aromatic polycarbonate resin composition in which the composition ratio of B component (B parts by weight) and the composition ratio of C component (C parts by weight) per 100 parts by weight of component A satisfy the following formula (I) is used as OA equipment. Or the method used for the exterior material of household appliances.
0.4 × B ≦ C ≦ 1.2 × B (I) The method according to claim 2, wherein the composition ratio of B component (B parts by weight) and the composition ratio of D component (D parts by weight) per 100 parts by weight of component A are in a range satisfying the following formula (II).
0.05 × B ≦ D ≦ 10 × B (II) The aromatic polycarbonate resin composition further contains 0.001 to 1 part by weight of (E) a phosphorus-based stabilizer (E component) per 100 parts by weight of the A component. Method. The method according to any one of claims 2 to 4, wherein the component D is a compound not containing a chlorine atom and a bromine atom. The method according to claim 2, wherein the component D is a phosphate ester flame retardant. The said A component is a method of any one of Claims 1-6 which contains the recycled aromatic polycarbonate resin 5weight% or more in 100 weight% of A component.

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