JP5432046B2 - Aromatic polycarbonate resin composition and molded article thereof - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition. More specifically, it is a resin composition containing a specific ratio of an aromatic polycarbonate resin, a polylactic acid resin and / or a copolymer of lactic acid and other hydroxycarboxylic acid, and a phenoxy resin with a low environmental load, and is resistant to hydrolysis. The present invention relates to an aromatic polycarbonate resin composition having excellent heat resistance and heat resistance, and having no deterioration in molding processability and molded product appearance due to thickening, and a molded product thereof. Furthermore, the present invention is a resin composition containing a specific ratio of an aromatic polycarbonate resin, a polylactic acid resin having a low environmental load and / or a copolymer of lactic acid and other hydroxycarboxylic acid, a phenoxy resin and a flame retardant. The present invention relates to an aromatic polycarbonate resin composition having the above-mentioned characteristics while having high flame retardancy required for materials for electric and electronic equipment, and molded articles thereof.

  Aromatic polycarbonate has excellent heat resistance, mechanical properties, impact resistance, dimensional stability, and the like, and is widely used in applications such as the OA equipment field, automobile field, and electric / electronic parts field. In addition, an inorganic filler has been widely mixed with an aromatic polycarbonate resin for the purpose of improving rigidity and strength. On the other hand, aromatic polycarbonate also has an aspect that most of the raw materials depend on petroleum resources. In recent years, due to concerns about the depletion of petroleum resources and the problem of increasing carbon dioxide in the air that causes global warming, there is a biomass resource that has a carbon neutral that does not depend on petroleum as a raw material and does not increase carbon dioxide even when burned. In the polymer field, biomass plastics produced from biomass resources have been actively developed. Polylactic acid resin is well known as a biomass plastic, and since it has relatively high heat resistance and mechanical properties among biomass plastics, its use is expanding to tableware, packaging materials, sundries, etc. The possibility of this has been studied. 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 an aromatic polycarbonate resin and a polylactic acid resin, and a pearly luster with good resin composition. It is also well known that it has excellent fluidity, heat resistance, rigidity and the like (see Patent Document 2). 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). Furthermore, it is also known that a resin composition in which mixing unevenness is eliminated can be obtained by blending other aliphatic polyester and a specific inorganic filler with polylactic acid (see Patent Document 4). However, due to its low hydrolysis resistance, polylactic acid resin has not been developed to industrial materials such as electrical / electronic parts and automobile parts that use engineering plastics.

  An epoxy compound is added to an aliphatic polyester as a hydrolysis resistance inhibitor, and at least a part of the carboxyl group ends are blocked to suppress a decrease in strength due to hot water treatment (see Patent Document 5), but it is developed as an industrial material. For this purpose, the level of hydrolysis resistance is insufficient, and there is a concern that the appearance may be deteriorated due to a decrease in heat resistance or thickening.

  Moreover, the technique which improves hydrolysis resistance by mix | blending a stabilizer including carbodiimide compound and antioxidant with respect to polylactic acid resin is shown (refer patent document 6), but a carbodiimide compound is polyester. As a result of the reaction of bonding to the end of the compound, the compound having an isocyanate group is liberated, generating a unique odor of the isocyanate compound and deteriorating the working environment.

JP 7-506863 A JP-A-7-109413 JP-A-11-140292 JP 2002-105298 A JP 2001-335626 A JP 2005-53870 A

  A first object of the present invention is to provide an aromatic polycarbonate resin composition that is excellent in hydrolysis resistance and heat resistance, and has no deterioration in molding processability and molded product appearance due to thickening, and a molded product thereof. . 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 that it has high flame retardancy, is excellent in hydrolysis resistance and heat resistance, has no deterioration in molding processability and molded product appearance due to thickening, and has an environmental impact. It is an object to provide a reduced aromatic polycarbonate resin composition and a molded article thereof.

  As a result of diligent research to achieve the above object, the present inventors have included a specific ratio of aromatic polycarbonate, a polylactic acid and / or a copolymer of lactic acid with other environmentally low carboxylic acids and a phenoxy resin with a low environmental load. The resin composition has surprisingly good hydrolysis resistance and heat resistance, and has no deterioration in molding processability and molded product appearance due to thickening, and the above-mentioned first object is achieved. It was found that the product and its molded product can be obtained. Furthermore, it discovered that the above-mentioned 2nd and 3rd objective can be achieved by combining a flame retardant of a specific ratio with respect to this composition. The present inventors have completed the present invention based on such knowledge.

That is, the present invention
(1) 100 parts by weight of (A) aromatic polycarbonate resin (component A), (B) copolymer of polylactic acid resin and / or lactic acid and other hydroxycarboxylic acid (component B) 10 to 100 weight Part and (C) phenoxy resin (C component) 0.001 to 10 parts by weight of a resin composition.
(2) It is a resin composition as described in the said structure (1) containing 0.01-2 weight part of (D) antioxidant (D component) with respect to 100 weight part of A component.
(3) The component D is at least one antioxidant selected from the group consisting of a phosphite compound, a phosphonite compound, a hindered phenol compound, and a thioether compound, according to the above configuration (1) or (2) It is a resin composition.
(4) The resin composition according to any one of the above constitutions (1) to (3), containing 0.1 to 100 parts by weight of (E) a flame retardant (E component) with respect to 100 parts by weight of the A component. .
(5) The resin composition according to any one of the above constitutions (1) to (4), which contains 0.1 to 100 parts by weight of (F) inorganic filler (F component) with respect to 100 parts by weight of component A. is there.
(6) A molded article comprising the resin composition according to any one of the configurations (1) to (5).
(7) The molded article according to the above configuration (6), which is molded by at least one molding method selected from the group consisting of injection molding, extrusion molding, thermoforming, blow molding and foam molding.
(8) The molded article according to the above configuration (6) or (7), which is a part selected from the group consisting of automobile parts, electrical / electronic parts, electrical equipment exterior parts, and OA exterior parts.

  The aromatic polycarbonate resin composition of the present invention and the molded product thereof are excellent in hydrolysis resistance and heat resistance, and without being deteriorated in molding processability and appearance of the molded product due to thickening. By combining a proportion of the flame retardant, the resin material has a high level of flame retardancy, so that it is possible to provide a resin material with a reduced environmental load applicable to a wide range of applications. Such applications include, for example, personal computers, notebook computers, game machines (home game machines, arcade game machines, pachinko machines, slot machines, etc.), display devices (LCD, organic EL, electronic paper, plasma display, projectors, etc.) , Power transmission parts (represented by dielectric coil power transmission device housings), printers, copiers, scanners and fax machines (including these multifunction devices), VTR cameras, optical film cameras, digital still cameras, camera lens units Examples thereof include precision devices such as security devices and mobile phones. In particular, the resin composition of the present invention is suitably used for OA equipment such as personal computers, notebook computers, game machines, display devices, printers, copiers, scanners and fax machines, and housings, covers, and frames of information processing devices. . In addition, the resin composition of the present invention is equipped with medical devices such as massage machines and high oxygen treatment devices, image recorders (so-called DVD recorders, etc.), audio appliances, home electric appliances such as electronic musical instruments, and precision sensors. It is also suitable for parts such as home robots. In addition, the resin composition of the present invention is used to transport various vehicle parts, batteries, power generation devices, circuit boards, integrated circuit molds, optical disk boards, disk cartridges, optical cards, IC memory cards, connectors, cable couplers, and electronic parts. Containers (IC magazine cases, silicon wafer containers, glass substrate storage containers, carrier tapes, etc.), antistatic or antistatic parts (e.g., charging rolls for electrophotographic photosensitive devices), and various mechanical parts (gears, turntables, It can be used for rotors and screws (including mechanical parts for micromachines). Therefore, the resin composition of the present invention is extremely useful for various industrial uses such as the field of OA equipment and the field of electrical and electronic equipment, and the industrial effect exerted by the resin composition is extremely large.

It is the surface side front schematic diagram of the molded article imitating the housing of the notebook computer used in the Example. (Length 140 mm x width 215 mm x edge height 10 mm, thickness 1.2 mm)

(Component A: aromatic polycarbonate resin)
The polycarbonate resin used as the component A in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly called 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 Den) diphenol, 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, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Examples include fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of excellent toughness and deformation characteristics, and is widely used.
In the present invention, in addition to the general-purpose polycarbonate bisphenol A-based polycarbonate, a special polycarbonate produced using other dihydric phenols can be used 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) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%), and A copolymeric polycarbonate in which the BCF component is 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the BPA component is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%), and A copolymeric polycarbonate in which the BCF component is 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%), and Copolymer polycarbonate in which the Bis-TMC component 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, etc. 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%, preferably 0.06 to 0.13% and Tg of 120 to 180 ° C, or (ii) Tg of 160 to 250 ° C, Polycarbonate which is preferably 170 to 230 ° C. and has a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

  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.

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

  In producing a polycarbonate resin by interfacial polymerization of the above dihydric phenol and carbonate precursor, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, etc., as necessary. May be used. The polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. And a copolymer polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with the bifunctional carboxylic acid and the bifunctional alcohol together. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

  The branched polycarbonate resin increases the melt tension of the resin composition of the present invention, and can improve the molding processability in extrusion molding, foam molding and blow molding based on such properties. As a result, a molded product by these molding methods, which is superior in dimensional accuracy, is obtained.

  Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2,4,6- Trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1 , 1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, and 4- {4- [1,1- Trisphenol such as bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol is preferably exemplified. Other polyfunctional aromatic compounds include phloroglucin, phloroglucid, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene. And trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and acid chlorides thereof. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4- Hydroxyphenyl) ethane is preferred.

  The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate resin is preferably in a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. Is 0.03 to 1 mol%, more preferably 0.07 to 0.7 mol%, particularly preferably 0.1 to 0.4 mol%.

Further, such a branched structural unit is not only derived from a polyfunctional aromatic compound but also derived without using a polyfunctional aromatic compound, such as a side reaction during a melt transesterification reaction. Also good. The ratio of such a branched structure can be calculated by ¹ H-NMR measurement.

  In addition, the aromatic polycarbonate resin which is 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 difunctional alcohol. Moreover, the mixture which blended 2 or more types of the obtained polycarbonate may be used.

The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of aliphatic difunctional carboxylic acids include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and linear saturated aliphatic dicarboxylic acids such as icosanedioic acid, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as acids. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.
Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

  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 terminator differs, etc. can also be used.

  Reaction formats such as interfacial polymerization, melt transesterification, carbonate prepolymer solid-phase transesterification, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate resin of the present invention, are various documents and patents. This is a well-known method in gazettes.

In producing the resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1 × 10 ^{4 to} 5 × 10 ⁴ , more preferably 1.4 × 10 ^4. a to 3 × 10 ^4, more preferably from ^{1.4 × 10 4 ~2.4 × 10 4} . A polycarbonate resin having a viscosity average molecular weight of less than 1 × 10 ⁴ may not provide practically sufficient toughness and crack resistance. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity average molecular weight exceeding 5 × 10 ⁴ generally has a low versatility because it generally requires a high molding temperature or requires a special molding method. A high molding temperature tends to cause deterioration of the deformation characteristics and rheological characteristics of the resin composition.

The polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the above value (5 × 10 ⁴ ) increases the melt tension of the resin composition of the present invention, and molding in extrusion molding, foam molding and blow molding based on such characteristics. Processability can be improved. Such an improvement effect is even better than the branched polycarbonate.

As a more suitable aspect, the A component is an aromatic polycarbonate resin (A-1-1 component) having a viscosity average molecular weight of 7 × 10 ^{4 to} 3 × 10 ⁵ , and a viscosity average molecular weight of 1 × 10 ^{4 to} 3 × 10 ⁴ . An aromatic polycarbonate resin (A-1 component) consisting of an aromatic polycarbonate resin (A-1-2 component) and having a viscosity average molecular weight of 1.6 × 10 ^{4 to} 3.5 × 10 ⁴ (hereinafter referred to as “high” A molecular weight component-containing aromatic polycarbonate resin "may also be used).

In the high molecular weight component-containing aromatic polycarbonate resin (A-1 component), the molecular weight of the A-1-1 component is preferably 7 × 10 ⁴ to 2 × 10 ⁵ , more preferably 8 × 10 ⁴ to 2 × 10 ^5. More preferably, it is 1 × 10 ⁵ to 2 × 10 ⁵ , and particularly preferably 1 × 10 ^{5 to} 1.6 × 10 ⁵ . The molecular weight of the A-1-2 component is preferably 1.0 × 10 ^{4 to} 2.5 × 10 ⁴ , more preferably 1.1 × 10 ^{4 to} 2.4 × 10 ⁴ , and even more preferably 1.2 ×. 10 ^{4 to} 2.4 × 10 ⁴ , particularly preferably 1.2 × 10 ^{4 to} 2.3 × 10 ⁴ .

  The high molecular weight component-containing aromatic polycarbonate resin (component A-1) is obtained by mixing the components A-1-1 and A-1-2 at various ratios and adjusting them so as to satisfy a predetermined molecular weight range. Can do. Preferably, in 100% by weight of the A-1 component, the A-1-1 component is 2 to 40% by weight, more preferably the A-1-1 component is 3 to 30% by weight, and still more preferably The A-1-1 component is 4 to 20% by weight, and particularly preferably the A-1-1 component is 5 to 20% by weight.

  As the preparation method of the component A-1, (1) a method in which the components A-1-1 and A-1-2 are independently polymerized and mixed, and (2) JP-A-5-306336. The method of producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method, represented by the method shown in Japanese Patent Publication No. Gazette, in the same system, the aromatic polycarbonate resin of the present invention A- A method of producing so as to satisfy the conditions of one component, and (3) an aromatic polycarbonate resin obtained by the production method (production method of (2)), a separately produced A-1-1 component and / or Examples thereof include a method of mixing the A-1-2 component.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate resin is dissolved 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

  The calculation of the viscosity average molecular weight in the resin composition of the present invention is performed as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.

  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.

(B component: polylactic acid resin and / or copolymer of lactic acid and other hydroxycarboxylic acid)
Among the polylactic acid resins and copolymers of lactic acids and other hydroxycarboxylic acids used as the B component in the present invention, polylactic acid is synthesized by ring-opening polymerization from a cyclic dimer of lactic acid, usually called lactide. The production method thereof is disclosed in USP 1,995,970, USP 2,362,511, USP 2,683,136. Copolymers of lactic acids and other hydroxycarboxylic acids are usually synthesized by ring-opening polymerization from a cyclic ester intermediate of lactide and hydroxycarboxylic acid. US Pat. No. 3,635,956 and US Pat. It is disclosed. 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, 6-hydroxycaproic acid and other hydroxycarboxylic acids, ethylene glycol, propylene Glycols, butanediol, neopentyl glycol, polyethylene glycol, glycerin, pentaerythritol and other compounds containing multiple hydroxyl groups in the molecule or derivatives thereof, succinic acid, adipic acid, sebacic acid, fumaric acid, terephthalic acid, isophthalic acid Examples thereof include compounds containing a plurality of carboxylic acid groups in the molecule, such as acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, and 5-tetrabutylphosphonium sulfoisophthalic acid, or derivatives thereof. In the production of the lactic acid resin, an appropriate molecular weight regulator, branching agent, other modifiers, 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 of only lactic acids, is preferably used. Poly-L lactic acid resin mainly composed of L-lactic acid units, poly-D lactic acid resin mainly composed of D-lactic acid units, or a mixture thereof. Any of them may be used.

  The weight average molecular weights of the poly L-lactic acid resin and the poly D-lactic acid resin are preferably 80,000 to 300,000, more preferably 100,000 to 250,000, in order to achieve both the mechanical properties and moldability of the composition of the present invention. Preferably, a range of 120,000 to 230,000 is selected.

  Although content of B component is 10-100 weight part with respect to 100 weight part of A component, 15-80 weight part is preferable and 20-60 weight part is more preferable. When the content is less than 10 parts by weight, the environmental load is not sufficiently reduced. When the content exceeds 100 parts by weight, the strength, heat resistance, and hydrolysis resistance are significantly reduced.

(C component: phenoxy resin)
The resin composition of the present invention contains a phenoxy resin as the C component. By including a phenoxy resin as a hydrolysis inhibitor, a molded article having improved hydrolysis resistance can be obtained.

  The C component phenoxy resin is a polymer in which the main chain is linked by a polyaddition structure of an aromatic diol and an aromatic diglycidyl ether, and has an average of more than 1 and less than 2 epoxy groups in the molecule. On the other hand, the epoxy resin conventionally used as a hydrolysis inhibitor has two or more epoxy groups in the molecule. These hydrolysis inhibitors contain two or more epoxy groups, and when the epoxy equivalent is small, there is a concern about deterioration of molding processability due to thickening and deterioration of the appearance of the molded product. Moreover, there is a concern that oligomers having a small molecular weight may adversely affect heat resistance and flame retardancy. That is, these conventional hydrolysis inhibitors are excellent in hydrolysis resistance and heat resistance, have no deterioration in molding processability and appearance of molded products, and have high flame retardance. On the other hand, by using a phenoxy resin, it is possible to obtain a molded product having excellent hydrolysis resistance and heat resistance, no deterioration in molding processability and appearance of the molded product, and high flame retardancy.

  Phenoxy resins are conventionally used in solution or without solvent using (1) condensation / polyaddition reaction of aromatic diol and epihalohydrin, and (2) polyaddition reaction of aromatic diol and aromatic diglycidyl ether. It can be obtained by condensation and polyaddition by a known method.

  Examples of the aromatic diol include hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ketone, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxy). Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2 -Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) ) Propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, , 3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, 2,2-bis (4-hydroxyphenyl) -1,1 1,3,3,3-hexafluoropropane and the like. Examples of the aromatic diglycidyl ether include hydroquinone diglycidyl ether, resorcin diglycidyl ether, bisphenol S diglycidyl ether, bisphenol K diglycidyl ether, bisphenol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, Methylhydroquinone diglycidyl ether, chlorohydroquinone diglycidyl ether, 4,4'-dihydroxydiphenyl oxide diglycidyl ether, 2,6-dihydroxynaphthalenediglycidyl ether, dichlorobisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, tetra Bromobisphenol A diglycidyl ether, bisphenol ACP Examples include diglycidyl ether, bisphenol L diglycidyl ether, and bisphenol V diglycidyl ether. One of these dihydroxy compounds and / or diglycidyl ether compounds may be used alone, or two or more thereof may be used in combination as a copolymer. Among such phenoxy resins, a phenoxy resin obtained from bisphenol A and epichlorohydrin is particularly preferable because it has a bisphenol A skeleton and is believed to increase the affinity with an aromatic polycarbonate.

  The weight average molecular weight of the phenoxy resin in the present invention is preferably 10,000 to 100,000, more preferably 25,000 to 85,000, and particularly preferably 40,000 to 60,000. When the weight average molecular weight is less than 10,000, the heat resistance and flame retardancy are deteriorated, and when it is greater than 100,000, the hydrolysis resistance is deteriorated and it is difficult to produce industrially. . The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (GPC) using tetrahydroxyfuran as a solvent and converted by a calibration curve using standard polystyrene.

  Furthermore, the epoxy equivalent of the phenoxy resin in the present invention is preferably 1,000 g / eq to 10,000 g / eq, more preferably 3,000 g / eq to 10,000 g / eq, and 5,000 g / eq to 10,000 g / eq. eq is particularly preferred. When the epoxy equivalent is less than 1,000 g / eq, the heat resistance and flame retardancy deteriorate when the weight average molecular weight is less than 10,000, and when the weight average molecular weight is greater than 10,000, aggregates are formed on the surface of the molded product. The appearance is deteriorated. In addition, when the epoxy equivalent is greater than 10,000 g / eq, hydrolysis resistance deteriorates regardless of the weight average molecular weight, which is not preferable. The epoxy equivalent in the present invention is a method in which a phenoxy compound is dissolved in pyridine, 0.05N hydrochloric acid is added and heated at 45 ° C., followed by back titration with 0.05N caustic soda using a mixture of thymol blue and cresol red as an indicator. It can ask for.

  Although content of C component is 0.001-10 weight part with respect to 100 weight part of A component, 0.01-10 weight part is preferable and 0.1-10 weight part is more preferable. When the content is less than 0.001 part by weight, the effect of the resin composition of the present invention on hydrolysis resistance is not sufficient, and when it exceeds 10 parts by weight, the heat resistance is deteriorated and the flame retardancy is deteriorated. Unfavorable because it has an adverse effect.

(D component: antioxidant)
The resin composition of the present invention may contain an antioxidant as the D component. As this antioxidant, at least one antioxidant selected from the group consisting of hindered phenol compounds, phosphite compounds, phosphonite compounds and thioether compounds is preferably used. By blending an antioxidant, not only is the hue and fluidity at the time of molding stabilized, it is also effective in improving hydrolysis resistance.

  Examples of the hindered phenol compound include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate. 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebi (2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) ) 2,2′-ethylidene-bis (4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3- Methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- ( -Tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1 , 1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4 , 4′-di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol) ), 2,2-thiodiethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy -3 ′, 5′-di-tert-butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl Phenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl) 4-hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like. Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) is used in the present invention. 4-hydroxyphenyl) propionate and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5,5] undecane is preferably used. Particularly preferred is octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. All of these are readily available. The said hindered phenol type compound can be used individually or in combination of 2 or more types.

  Phosphite compounds include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl mono Phenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) ) Phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentae Thritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A penta Examples include erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexylpentaerythritol diphosphite. Furthermore, as other phosphite compounds, those 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 (4,6-di-tert-butylphenyl) octyl phosphite, and the like. Suitable phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methyl). Phenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite. All of these are readily available. The above phosphite compounds can be used alone or in combination of two or more.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylene diphospho Knight, 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- -Tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) Examples include -4-phenyl-phenyl phosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenyl phosphonite. Tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferred, and tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite Knight and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred. 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. The phosphonite compound is preferably tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, and stabilizers based on the phosphonite are Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos. P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) is commercially available and any of them can be used. The said phosphonite type compound can be used individually or in combination of 2 or more types.

  Specific examples of thioether compounds include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-lauryl thiopropionate), Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthio) Propionate) and the like. The said thioether type compound can be used individually or in combination of 2 or more types.

  The content of the antioxidant 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 1 part by weight with respect to 100 parts by weight of the component A. Part. When the content is less than 0.01 parts by weight, the antioxidant effect is insufficient, and not only the hue and fluidity during molding process become unstable, but also hydrolysis resistance may be deteriorated. In addition, when the content is more than 2 parts by weight, the reaction component derived from the antioxidant may be deteriorated and the hydrolysis resistance may be deteriorated.

  Further, it is preferable to use a combination of one or more of the hindered phenol compounds and phosphite compounds, phosphonite compounds, and thioether compounds. By using a combination of one or more of hindered phenol compounds and phosphite compounds, phosphonite compounds, and thioether compounds, a synergistic effect as a stabilizer is exhibited, and hue and flow during molding are more enhanced. It is effective in stabilizing the properties and improving the hydrolysis resistance.

(E component: flame retardant)
The composition of the present invention can contain a flame retardant as the E component. The flame retardant is not particularly limited as long as it is a substance added for the purpose of imparting flame retardancy to the resin. Brominated flame retardant, phosphorus flame retardant, nitrogen compound flame retardant, silicone flame retardant, Examples thereof include organic metal salt flame retardants, metal hydroxide compound flame retardants, and the like. These may be used alone or in combination of two or more, and one or more compounds may be used in each type. It is preferable to use it properly according to the purpose.

(E-1 component: brominated flame retardant)
Specific examples of the brominated flame retardant used in the present invention include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis (2,4,6-tribromo). Phenoxy) ethane, ethylenebistetrabromophthalimide, hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol-S, Tris (2,3-dibromopropyl-1) isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobis Enol-A, tetrabromobisphenol-A derivative, tetrabromobisphenol-A-epoxy oligomer or polymer, tetrabromobisphenol-A-carbonate oligomer or polymer, brominated epoxy resin such as brominated phenol novolac epoxy, tetrabromobisphenol-A -Bis (2-hydroxydiethyl ether), tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, Tris (tribromoneopentyl) phosphate, poly (pentabromobenzylpolyacrylate), octabromotrimethylphenylindane, dibromoneope Chill glycol, pentabromobenzyl polyacrylate, dibromo cresyl glycidyl ether, N, N'ethylene - bis - such as tetrabromo phthalic imide. Of these, tetrabromobisphenol-A-epoxy oligomer, tetrabromobisphenol-A-carbonate oligomer, and brominated epoxy resin are preferable.

(E-2 component: phosphorus flame retardant)
Phosphorus flame retardants include (1) phosphate ester flame retardant, (2) phosphonitrile flame retardant, (3) phosphonate flame retardant, (4) polyphosphate flame retardant, (5) phosphinate System, (6) red phosphorus.

(1) Phosphate ester flame retardant Specific examples of the phosphate ester flame retardant include one or more phosphate ester compounds represented by the following formula (1).

In the formula, X ¹ represents hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4- Hydroxyphenyl) is a group derived from sulfide. n ¹ is an integer of 0 to 5, or when n number of different mixtures of phosphoric acid ester is an average value of 0 to 5. R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently derived from phenol, cresol, xylenol, isopropylphenol, butylphenol, p-cumylphenol substituted or unsubstituted with one or more halogen atoms. It is a group.

More preferably, X ¹ in the formula is a group derived from hydroquinone, resorcinol, bisphenol A, and dihydroxydiphenyl, n ¹ is an integer of ¹ to 3, or n ¹ number of different phosphoric acids In the case of a blend of esters, it is the average value, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently a phenol, cresol that is substituted or more preferably substituted with one or more halogen atoms And 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.

(2) Phosphononitrile-based flame retardant The phosphonitrile-based flame retardant used in the present invention is a phosphonitrile linear polymer and / or a cyclic polymer, and is an oligomer or polymer having a repeating unit represented by the following formula (2). The number average degree of polymerization is 3 or more. Although it may be either linear or cyclic, a cyclic trimer is particularly preferably used. Further, it may be a mixture in which a linear product and a cyclic product are mixed at an arbitrary ratio.

In the formula, A and B each independently represent an O, N, or S atom. R ²¹ and R ²² are each independently an aryl group having 6 to 15 carbon atoms, an alkyl group having 6 to 15 carbon atoms, an aralkyl group having 6 to 15 carbon atoms, or a cycloalkyl group having 6 to 15 carbon atoms. A ring structure in which R ²¹ and R ²² are linked may be used. x ¹ and y ¹ are 0 or 1. n ² means a number average degree of polymerization and represents a value of 3 or more.

  Such phosphonitrile linear polymers and / or cyclic polymers include hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, or poly (dichlorophosphazene) obtained by ring-opening polymerization of these cyclic oligomers and alcohol, phenol, amine, thiol, It can be synthesized by reacting with a nucleophilic reagent such as a Grignard reagent by a known method.

(3) Phosphonate flame retardant The phosphonate flame retardant is preferably represented by the following general formula (3).

In the formula, each of R ³¹ and R ³² is independently a branched or unbranched alkylene group having 1 to 24 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or non-substituted group having 6 to 30 carbon atoms. A substituted aralkylene group, or a substituted or unsubstituted alkarylene group having 6 to 30 carbon atoms.

R ³³ is a hydrogen atom, a branched or unbranched alkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, Or it is a C6-C30 substituted or unsubstituted alkaryl group. x ² and ^{y 2} are the number of independently 1 to 50.

(4) Polyphosphate flame retardant Examples of the polyphosphate flame retardant used in the present invention include ammonium polyphosphate and melamine polyphosphate.

(5) Phosphinate Flame Retardant Examples of the phosphinate flame retardant used in the present invention include salts represented by the following formula (4) or the following formula (5).

In the formula, each of R ⁴¹ and R ⁴² independently represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms. Is an aralkyl group. R ⁴³ represents a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 6 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylene arylene group having 7 to 20 carbon atoms, or a cycloalkylene arylene group. It is a group. M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zn, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base. x ³ is 1 or 2. m is 2 or 3, and n ³ is 1 or 3.

R ⁴¹ and R ⁴² appropriately maintain the phosphorus content in the flame retardant and suitably express the flame retardancy, and at the same time suitably express the crystallinity of the composition. A linear or branched alkyl group, cycloalkyl group, aryl group or aralkyl group in the range of is preferably selected. Of these, an alkyl group and an aryl group are preferably selected. Specifically, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, or a phenyl group is preferably exemplified.

R ⁴³ appropriately maintains the phosphorus content in the flame retardant and suitably expresses the flame retardancy, and at the same time suitably expresses the crystallinity of the composition. Therefore, R ⁴³ is a straight chain having 1 to 10 carbon atoms. Alternatively, a branched alkylene group, cycloalkylene group, arylene group, alkylene arylene group or cycloalkylene arylene group is preferably selected.

  Specifically, for example, methylene group, ethylene group, methylethane-1,3-diyl group, propane-1,3-diyl group, 2,2-dimethylpropane-1,3-diyl group, butane-1,4-diyl Group, octane-1,8-diyl group, phenylene group, naphthylene group, ethylphenylene group, tert-butylphenylene group, methylnaphthylene group, ethylnaphthylene group, phenylenemethylene group, phenyleneethylene group, phenylenepropylene group, phenylenebutylene group Etc. are exemplified.

M represents Mg, Ca, Al, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base. When there are a plurality of M, each is independently selected. Examples of protonated nitrogen bases include amide groups, ammonium groups, alkylammonium groups, and melamine-derived groups. In order to improve the flame retardancy, crystallinity, moldability, etc. of the composition of the present invention, M is selected from the group of Mg, Ca, Al, Zn and groups derived from amide groups, ammonium groups, alkylammonium groups or melamines. The Of these, Al is most preferably selected.
When the phosphinates represented by the formulas (4) and (5) are used in combination, the weight ratio of (4) / (5) is preferably selected in the range of 10/90 to 30/70.

(6) Red phosphorus As red phosphorus, not only untreated red phosphorus but also one or more compound films selected from the group consisting of thermosetting resin coatings, metal hydroxide coatings, and metal plating coatings were used. Red phosphorus can be preferably used. The thermosetting resin of the thermosetting resin film is not particularly limited as long as it is a resin capable of coating red phosphorus. For example, phenol-formalin resin, urea-formalin resin, melamine-formalin resin, alkyd resin Etc. The metal hydroxide film is not particularly limited as long as it is a resin capable of coating red phosphorus, and examples thereof include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. . The metal of the metal plating film is not particularly limited as long as it is a resin capable of coating red phosphorus, and examples thereof include Fe, Ni, Co, Cu, Zn, Mn, Ti, Zr, Al, and alloys thereof. Furthermore, these coatings may be laminated in combination of two or more or in combination of two or more.
Among the phosphorous flame retardants, phosphate ester flame retardants, phosphonate flame retardants, polyphosphate flame retardants and phosphinate salts are preferable, and phosphate ester flame retardants are particularly preferable.

(E-3 component: nitrogen-based flame retardant)
The nitrogen-based flame retardant used in the present invention is a nitrogen-based flame retardant containing a triazine skeleton, and is an agent that synergistically increases the flame retardancy of the phosphorus-based flame retardant. From the following formulas (6) and (7) At least one selected from the group consisting of is applied.

In the formula, R ^{51 to} R ⁵³ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 16 carbon atoms, (these are not substituted, hydroxyl groups or 1 to 4), an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an acyl group, an acyloxy group, an aryl group having 6 to 12 carbon atoms, -O-RA , -N (RA) (RB) or a group represented by N-alicyclic or N-aromatic -N (RA) RB. Here, RA and RB are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a -cycloalkyl group having 5 to 16 carbon atoms (these are not substituted, a hydroxyl group or a hydroxyalkyl having 1 to 4 carbon atoms). Substituted with a functional group), an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an acyl group, an acyloxy group, or an aryl group having 6 to 12 carbon atoms.

However, all of R ^{51 to} R ⁵³ are not simultaneously hydrogen atoms and all of R ^{51 to} R ⁵³ are not simultaneously —NH ₂ in the formula (6). X ² is an acid capable of forming an adduct with the melamine or triazine compound (6), and s and t are each independently 1 or 2.

In Formula (6), when at least one of R ^{51 to} R ⁵³ is an aryl group having 6 to 12 carbon atoms, the flame retardancy can be more effectively enhanced when blended with a phosphinate in a phosphorus flame retardant. In addition, the flame retardancy, crystallinity and moldability of the composition of the present invention can be improved more suitably.

In the formula (7), when all of R ^{51 to} R ⁵³ are —N (RA) (RB), the flame retardancy can be increased more effectively, and the flame retardancy and crystal of the composition of the present invention can be improved. And moldability can be improved more suitably.

  Preferred examples of (6) and (7) include dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate, melon polyphosphate, and the like.

  In the present invention, the flame retardancy of the composition of the present invention is improved by additionally using at least one of the compounds represented by the following formulas (8) to (11) in addition to the nitrogen-based flame retardant having a triazine skeleton. Can be made.

In the formula, R ^{61 to} R ⁷⁶ are each preferably independently exemplified by the functional groups described as R ^{51 to} R ⁵³ . For example, tris (hydroxyethyl) isocyanurate, allanin, glycoluril, urea. Cyanurate and the like are preferably exemplified. Such an agent is applied in the range of 10 to 50% by weight based on the nitrogen-based flame retardant containing a triazine skeleton.

(E-4 component: silicone flame retardant)
Examples of the silicone flame retardant used in the present invention include silicone resins and silicone oils. Examples of the silicone resin include a resin having a three-dimensional network structure formed by combining structural units of SiO ₂ , RSiO _3/2 , R ₂ SiO, and R ₃ SiO _1/2 . Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent. In the silicone oil, polydimethylsiloxane, and at least one methyl group at the side chain or terminal of polydimethylsiloxane is a hydrogen element, an alkyl group, a cyclohexyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, or a polyether group. , A modified polysiloxane modified with at least one group selected from a carboxyl group, a mercapto group, a chloroalkyl group, an alkyl higher alcohol ester group, an alcohol group, an aralkyl group, a vinyl group, or a trifluoromethyl group, or a mixture thereof Can be mentioned.

(E-5 component: organometallic salt flame retardant)
The organometallic salt flame retardant is advantageous in that the heat resistance is substantially maintained and an antistatic property can be imparted. The organometallic salt flame retardant most advantageously used in the present invention is a fluorine-containing organometallic salt compound. The fluorine-containing organometallic salt compound of the present invention refers to a metal salt compound comprising an anion component composed of an organic acid having a fluorine-substituted hydrocarbon group and a cation component composed of a metal ion. More preferred specific examples include metal salts of fluorine-substituted organic sulfonic acids, metal salts of fluorine-substituted organic sulfates, and metal salts of fluorine-substituted organic phosphates. Fluorine-containing organometallic salt compounds can be used alone or in combination of two or more. Among them, a metal salt of a fluorine-substituted organic sulfonic acid is preferable, and a metal salt of a sulfonic acid having a perfluoroalkyl group is particularly preferable. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8.

  The metal constituting the metal ion of the organometallic salt flame retardant is an alkali metal or an alkaline earth metal. Examples of the alkali metal include lithium, sodium, potassium, rubidium and cesium. Examples of the alkaline earth metal include beryllium. , Magnesium, calcium, strontium and barium. More preferred is an alkali metal. Accordingly, a preferred organometallic salt flame retardant is an alkali metal perfluoroalkyl sulfonate. Among such alkali metals, rubidium and cesium are suitable when transparency requirements are higher, but these are not general-purpose and difficult to purify, resulting in disadvantages in terms of cost. is there. On the other hand, although lithium and sodium are advantageous in terms of cost and flame retardancy, they may be disadvantageous in terms of transparency. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, but perfluoroalkylsulfonic acid potassium salt having an excellent balance of properties is most suitable in any respect. Such potassium salts and alkali metal salts of perfluoroalkylsulfonic acid composed of other alkali metals can be used in combination.

  Such alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, perfluorobutanesulfone. Acid sodium, sodium perfluorooctane sulfonate, lithium trifluoromethane sulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethane sulfonate, cesium perfluorobutane sulfonate, cesium perfluorooctane sulfonate, Cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perful B hexane sulfonate rubidium, and these may be used in combination of at least one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

  The fluorine-containing organometallic salt preferably has a fluoride ion content as measured by ion chromatography of 50 ppm or less, more preferably 20 ppm or less, and even more preferably 10 ppm or less. The lower the fluoride ion content, the better the flame retardancy and light resistance. The lower limit of the fluoride ion content can be substantially zero, but is practically preferably about 0.2 ppm in view of the balance between the refining man-hour and the effect. Such alkali metal salt of perfluoroalkylsulfonic acid having a fluoride ion content is purified, for example, as follows. The perfluoroalkylsulfonic acid alkali metal salt is dissolved in 2 to 10 times by weight of the metal salt in ion-exchanged water in the range of 40 to 90 ° C. (more preferably 60 to 85 ° C.). The alkali metal salt of perfluoroalkylsulfonic acid is a method of neutralizing perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, or perfluoroalkylsulfonyl fluoride with an alkali metal carbonate or hydroxide. It is produced by a neutralizing method (more preferably by the latter method). The ion-exchanged water is particularly preferably water having an electric resistance value of 18 MΩ · cm or more. The solution in which the metal salt is dissolved is stirred at the above temperature for 0.1 to 3 hours, more preferably 0.5 to 2.5 hours. Thereafter, the liquid is cooled to 0 to 40 ° C, more preferably in the range of 10 to 35 ° C. Crystals precipitate upon cooling. The precipitated crystals are removed by filtration. This produces a suitable purified perfluoroalkylsulfonic acid alkali metal salt.

  In addition, as an organic metal salt flame retardant other than the above-mentioned fluorine-containing organic metal salt compound, a metal salt of an organic sulfonic acid not containing a fluorine atom is suitable. Examples of the metal salt include an alkali metal salt of an aliphatic sulfonic acid, an alkaline earth metal salt of an aliphatic sulfonic acid, an alkali metal salt of an aromatic sulfonic acid, and an alkaline earth metal salt of an aromatic sulfonic acid (any Also does not contain a fluorine atom).

  Preferable examples of the aliphatic sulfonic acid metal salt include an alkali (earth) metal salt of an alkyl sulfonate, and these can be used alone or in combination of two or more (here, alkali The (earth) metal salt is used to include both alkali metal salts and alkaline earth metal salts). Preferred examples of the alkane sulfonic acid used for the alkali (earth) metal salt of the alkyl sulfonate include methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, methyl butane sulfonic acid, hexane sulfonic acid, and heptane. Examples thereof include sulfonic acid and octanesulfonic acid, and these can be used alone or in combination of two or more.

  The aromatic sulfonic acid used in the aromatic (earth) metal salt of aromatic sulfonate includes monomeric or polymeric aromatic sulfide sulfonic acid, aromatic carboxylic acid and ester sulfonic acid, monomeric or polymeric sulfonic acid. Aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonic acid, aromatic ketone sulfonic acid, heterocyclic sulfonic acid, Examples include at least one acid selected from the group consisting of sulfonic acids of aromatic sulfoxides and condensates of methylene type bonds of aromatic sulfonic acids, and these are used alone or in combination of two or more. be able to.

  Specific examples of the aromatic (earth) metal salt of an aromatic sulfonate include, for example, disodium diphenyl sulfide-4,4′-disulfonate, dipotassium diphenyl sulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate Poly (1,3-phenylene oxide) polysulfonic acid polysodium, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid poly Lithium, poly (2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2 , 6-disulfonic acid dipotassium, biphenyl-3,3'-disulfonic acid calcium, diphenylsulfone-3-sulfonic acid sodium, diphenylsulfone-3-sulfonic acid potassium, diphenylsulfone-3,3'-disulfonic acid dipotassium, diphenylsulfone Α, α, α-trifluoroacetophenone sodium 4-sulfonate, dipotassium benzophenone-3,3′-disulfonate, Nene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, naphthalene Examples thereof include a formalin condensate of sodium sulfonate and a formalin condensate of sodium anthracene sulfonate.

  On the other hand, the alkali (earth) metal salt of sulfate ester may include, in particular, the alkali (earth) metal salt of sulfate ester of monovalent and / or polyhydric alcohols. Alcohol sulfates include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono, di, tri, tetrasulfate, and lauric acid monoglyceride. And sulfuric acid esters of palmitic acid monoglyceride and stearic acid monoglyceride sulfate. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate.

Examples of other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N Examples include-(N'-benzylaminocarbonyl) sulfanilimide and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanilimide.
Among the above, preferable metal salts of organic sulfonic acids not containing fluorine atoms are aromatic (earth) metal salts of aromatic sulfonates, and potassium salts are particularly preferable.

(E-6 component: metal hydroxide compound flame retardant)
As the metal hydroxide compound-based flame retardant of the present invention, aluminum hydroxide, magnesium hydroxide and calcium hydroxide are preferable, and those having high purity are preferable in order to improve the thermal stability of the composition. What is 5% or more is preferable. The purity of the metal hydroxide compound flame retardant can be measured by a known method. For example, the content of impurities contained in the metal hydroxide compound flame retardant is measured by a known method, and the purity of the metal hydroxide compound flame retardant is obtained by subtracting the impurity content from the total amount. be able to. More specifically, for example, in the case of aluminum hydroxide, examples of impurities include Fe ₂ O ₃ , SiO ₂ , T—Na ₂ O, and S—Na ₂ O. The content of Fe ₂ O ₃ is determined by O-phenanthroline spectrophotometry (JIS H 1901) after melting in a sodium carbonate-boric acid solution. The content of SiO ₂ is determined by the molybdenum blue absorptiometry (JIS H 1901) after melting in sodium carbonate-boric acid solution. The content of T-Na ₂ O is obtained by a flame photometric method after melting in sulfuric acid, and S-Na ₂ O is obtained by a flame photometric method after extraction with hot water. The purity of the hydroxide can be obtained by reducing the content determined as described above from the weight of aluminum hydroxide. Of course, it is needless to say that different kinds of metal hydroxide compound flame retardants can be used in combination.

  The shape of the metal hydroxide compound flame retardant used in the present invention is not particularly limited, but is preferably granular. As for the particle diameter, it is preferable that the average particle diameter calculated | required by the laser diffraction method is about 100 micrometers or less. In this case, the particle size distribution does not matter. From the viewpoint of injection moldability in the molding process and dispersibility at the time of kneading, the average particle diameter is preferably in the above range, and more preferably in the above range. Of course, in order to increase the filling rate of the composition, a plurality of kinds of metal hydroxide compound flame retardants having different average particle diameters can be used in combination.

Furthermore, it is preferable to use particles having a BET specific surface area of about 5.0 m ² / g or less determined by a nitrogen gas adsorption method. Of course, in order to increase the filling rate into the composition, a plurality of kinds of metal hydroxide compound flame retardants having different BET specific surface areas can be used in combination. From the viewpoint of moldability, the BET specific surface area is preferably in the above range, and a smaller one is more preferable in the above range.

  The content of the E-1 component to the E-6 component is preferably 0.1 to 100 parts by weight, more preferably 3 to 90 parts by weight, still more preferably 5 to 80 parts by weight with respect to 100 parts by weight of the A component. It is. When the content is less than 0.1 parts by weight, the amount of the flame retardant added is too small and flame retardancy is not obtained. Since it worsens, it is not preferable.

(F component: inorganic filler)
As the inorganic filler which is the F component of the present invention, glass fiber, carbon fiber, glass flake, wollastonite, kaolin clay, mica, talc and various whiskers (potassium titanate whisker, aluminum borate whisker, etc.) are generally used. Various known fillers can be used. The shape of the inorganic filler can be freely selected from fibrous, flaky, spherical and hollow shapes, and fibrous and flaky materials are suitable for improving the strength and impact resistance of the resin composition.

  Among these, natural mineral pulverized products are likely to cause deterioration of hue, so the F component is preferably an inorganic filler made of natural mineral pulverized products, and more preferably inorganic materials made of silicate natural mineral pulverized products. Mica, talc, and wollastonite are preferable from the viewpoint of the shape of the filler. On the other hand, these inorganic fillers are non-petroleum resource materials as compared with petroleum resource materials such as carbon fiber, and therefore, raw materials with a lower environmental load are used. There is an effect that the significance of use is further enhanced.

  The average particle size of mica that can be used in the present invention is a number average particle size calculated by a number average of a total of 1000 particles observed with a scanning electron microscope and extracted those having a size of 1 μm or more. The number average particle diameter is preferably 10 to 500 μm, more preferably 30 to 400 μm, still more preferably 30 to 200 μm, and most preferably 35 to 80 μm. When the number average particle diameter is less than 10 μm, the impact strength may be lowered. On the other hand, if it exceeds 500 μm, the impact strength is improved, but the appearance tends to deteriorate. As the thickness of mica, one having a thickness measured by electron microscope observation of 0.01 to 10 μm can be preferably used. More preferably, 0.1 to 5 μm can be used. The aspect ratio is preferably 5 to 200, more preferably 10 to 100. The mica used is preferably mascobite mica, and its Mohs hardness is preferably about 3. Muscovite mica can achieve higher rigidity and strength than other mica such as phlogopite, and a more suitable aromatic polycarbonate resin composition is provided. In addition, as a method for pulverizing mica, a dry pulverization method of pulverizing raw mica ore with a dry pulverizer, and coarsely pulverizing mica rough ore with a dry pulverizer, followed by adding a grinding aid such as water in a slurry state There is a wet pulverization method in which main pulverization is performed by a wet pulverizer, followed by dehydration and drying. The mica of the present invention can be produced by any pulverization method, but the dry pulverization method is generally lower in cost. On the other hand, the wet pulverization method is effective for pulverizing mica more thinly and finely, but is expensive. Mica may be surface-treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes, and further granulated with sizing agents such as various resins, higher fatty acid esters, and waxes to form granules. May be.

The talc that can be used in the present invention is a scaly particle having a layered structure, which is a hydrous magnesium silicate in terms of chemical composition, and is generally represented by the chemical formula 4SiO ₂ .3MgO.2H ₂ O. the SiO ₂ 56-65 wt%, the MgO 28 to 35 wt%, and a _{H 2} O about 5 wt%. As other minor components, Fe ₂ O ₃ is 0.03 to 1.2% by weight, Al ₂ O ₃ is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K ₂ O. Is 0.2 wt% or less, Na ₂ O is 0.2 wt% or less, the specific gravity is about 2.7, and the Mohs hardness is 1. The average particle diameter of the talc of the present invention is preferably 0.5 to 30 μm. The average particle size is a particle size at a 50% stacking rate obtained from the particle size distribution measured by the Andreazen pipette method measured according to JIS M8016. The particle diameter of talc is more preferably 2 to 30 μm, further preferably 5 to 20 μm, and most preferably 10 to 20 μm. Talc in the range of 0.5 to 30 μm imparts good surface appearance and flame retardancy to the aromatic polycarbonate resin composition in addition to rigidity and low anisotropy. In addition, there is no particular limitation on the manufacturing method when talc is crushed from raw stone, and the axial flow mill method, the annular mill method, the roll mill method, the ball mill method, the jet mill method, the container rotary compression shearing mill method, etc. are used. can do. Furthermore, the talc after pulverization is preferably classified by various classifiers and has a uniform particle size distribution. There are no particular restrictions on the classifier, impactor type inertial force classifier (variable impactor, etc.), Coanda effect type inertial force classifier (elbow jet, etc.), centrifugal field classifier (multistage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator). Further, talc is preferably in an agglomerated state in view of its handleability and the like, and as such a production method, there are a method using degassing compression, a method using compression using a sizing agent, and the like. In particular, the degassing compression method is preferable in that the sizing agent resin component which is simple and unnecessary is not mixed into the resin composition of the present invention.

The wollastonite that can be used in the present invention is substantially represented by the chemical formula CaSiO ₃ , usually SiO ₂ is about 50 wt% or more, CaO is about 47 wt%, and other Fe ₂ O ₃ , Al ₂ O _3, etc. Is included. Wollastonite is a white acicular powder obtained by crushing and classifying raw wollastonite, and has a Mohs hardness of about 4.5. The average fiber diameter of wollastonite used is preferably 0.5 to 20 μm, more preferably 0.5 to 10 μm, and most preferably 1 to 5 μm. The average fiber diameter is observed by a scanning electron microscope, and is calculated by a number average of a total of 1000 samples having a diameter of 0.1 μm or more extracted.

  0.1-100 weight part is preferable with respect to 100 weight part of A component, as for content of F component, 1.0-80 weight part is more preferable, and 5-50 weight part is further more preferable. When the content is less than 0.1 parts by weight, the reinforcing effect on the mechanical properties of the resin composition of the present invention is not sufficient, and when it exceeds 100 parts by weight, the moldability and hue may deteriorate. This is not preferable.

(Other ingredients)
(Impact modifier)
The composition of the present invention may contain an impact modifier. By containing an impact modifier, a composition having excellent mechanical properties can be obtained.
An elastic polymer can be used as the impact modifier, and examples of the elastic polymer include a rubber component having a glass transition temperature of 10 ° C. or lower, aromatic vinyl, vinyl cyanide, acrylate ester, methacrylate ester, And a graft copolymer obtained by copolymerizing one or more monomers selected from vinyl compounds copolymerizable therewith. 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 acrylic copolymers, styrene / ethylene propylene / styrene elastomers (hydrogenated styrene / isoprene / styrene elastomers), and thermoplastic elastomers such as hydrogenated styrene / butadiene / styrene elastomers. Can be mentioned. 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 suitable as an impact modifier. 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 polymer preferably contains 40% or more of a rubber component, more preferably 60% or more.

  Such rubber components include 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 may include halogen atoms in view of concerns about the generation of harmful substances during combustion. A rubber component not contained 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.

  More preferred as the rubber component of the core-shell type graft copolymer suitable for the impact modifier is butadiene rubber. 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 content of the impact modifier is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 80 parts by weight with respect to 100 parts by weight of the component A. If the content is less than 0.1 parts by weight, the impact-modifying effect is not satisfactory, and if it exceeds 100 parts by weight, the heat resistance is deteriorated and the flame retardancy is adversely affected.

(Crystallization accelerator)
The composition of the present invention may contain a crystallization accelerator. By containing the crystallization accelerator, a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained. That is, the application of the crystallization accelerator improves the moldability and crystallinity of the polylactic acid resin and / or a copolymer of lactic acid and other hydroxycarboxylic acid (component B), and is sufficient even in normal injection molding. Crystallized products with excellent heat resistance and moist heat resistance can be obtained. In addition, the manufacturing time for manufacturing the molded product can be greatly shortened, and the economic effect is great.
As the crystallization accelerator, either an inorganic crystallization nucleating agent or an organic crystallization nucleating agent can be used.

  As inorganic crystallization nucleating agents, talc, kaolin, silica, synthetic mica, clay, zeolite, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium carbonate, calcium sulfate, barium sulfate, calcium sulfide, boron nitride , Montmorillonite, neodymium oxide, aluminum oxide, phenylphosphonate metal salt and the like. These inorganic crystallization nucleating agents are treated with various dispersing aids in order to enhance the dispersibility in the composition and the effect thereof, and are in a highly dispersed state with a primary particle size of about 0.01 to 0.5 μm. Are preferred.

  Organic crystallization nucleating agents include calcium benzoate, sodium benzoate, lithium benzoate, potassium benzoate, magnesium benzoate, barium benzoate, calcium oxalate, disodium terephthalate, dilithium terephthalate, dipotassium terephthalate, Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, barium myristate, sodium octacolate, calcium octacolate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate , Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicy Organic carboxylic acid metal salts such as zinc acid, aluminum dibenzoate, β-naphthoic acid sodium, β-naphthoic acid potassium, sodium cyclohexanecarboxylic acid and the like, and organic sulfonic acid metal salts such as sodium p-toluenesulfonate and sodium sulfoisophthalate. Can be mentioned. Also, organic carboxylic acid amides such as stearic acid amide, ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (tert-butylamide), low density polyethylene, high density polyethylene, polyiso Propylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, high melting point polylactic acid, sodium salt of ethylene-acrylic acid copolymer, sodium of styrene-maleic anhydride copolymer Examples thereof include salts (so-called ionomers), benzylidene sorbitol and derivatives thereof such as dibenzylidene sorbitol.

Among these, at least one selected from talc and organic carboxylic acid metal salts is preferably used. Only one type of crystallization nucleating agent may be used in the present invention, or two or more types may be used in combination.
The content of the crystallization accelerator is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the component A. If the content is less than 0.01 parts by weight, the effect of promoting crystallization is not sufficient, and if it exceeds 30 parts by weight, the mechanical properties are impaired.

  In the resin composition of the present invention, other thermoplastic resins (for example, polyalkylene terephthalate resin, polyarylate resin, liquid crystalline polyester resin, polyamide resin, polyimide resin, polyether, and the like are used as long as the object of the present invention is not impaired. Imide 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, epoxy resin, etc.), plasticizer (polyester type) Plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, phosphate ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers), ultraviolet absorbers (benzotriazoles, triazines, Benzophenone-based), 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 agents, inorganic And organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), infrared Absorbers, and photochromic agent ultraviolet absorber may be blended such as processing aids. These various additives can be used in known blending amounts when blended with the aromatic polycarbonate resin.

(Manufacture of resin composition)
Arbitrary methods are employ | adopted for manufacture of the aromatic polycarbonate resin composition of this invention. For example, components A to F are sufficiently mixed (so-called dry blend) using premixing means such as a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer, and then an extrusion granulator as necessary. Granulation of the pre-mixture obtained by using a briquetting machine, etc., and then melt-kneading with a melt-kneader typified by a vent type twin-screw extruder, and pelletizing the melt-kneaded composition with a device such as a pelletizer The method of making it.

  In addition, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder. As such a liquid injection device or a liquid addition device, one provided with a heating device is preferably used.

  The extruded resin can be cut directly into pellets or formed into strands and then cut into pellets with a pelletizer. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Although the shape of the obtained pellet can take general shapes, such as a cylinder, a prism, and a spherical shape, it is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

(Creation of molded products)
The resin composition of the present invention obtained as described above can usually produce various products by injection molding the pellets produced as described above. Further, the resin composition melt-kneaded by a twin screw extruder can be directly formed into a sheet, a film, a profile extrusion molded product, a direct blow molded product, and an injection molded product without going through pellets.

  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 addition, either a cold runner method or a hot runner method can be selected for molding. More preferable are injection compression molding and injection press molding which can be molded at a low injection speed.

  Moreover, the resin composition of this invention can also be used in the form of various profile extrusion-molded articles, a sheet | seat, a film, etc. 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. Moreover, you may make the resin composition of this invention into a molded article by rotational molding or blow molding.

  The resin composition of the present invention 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, commercial game machines, pachinko machines, slot machines, etc.), displays, etc. Molding devices such as 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 Goods are illustrated. 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. Using resin products formed from aromatic polycarbonate resin compositions Door can be. 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, various surface treatments can be performed on the molded article made of the resin composition of the present invention. Surface treatment here refers to 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. A method used for ordinary resins can be applied. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation).

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these. The evaluation was conducted on the following items. The following raw materials were used as raw materials.

[Examples 1-12, Comparative Examples 1-11]
1. Manufacture of composition pellets After the components shown in Tables 1 and 2, excluding the E and F-2 components, were dry blended in the proportions shown in Tables 1 and 2, supplied from the first supply port of the extruder did. When E component is added, the third supply port (first supply port and vent exhaust in the middle of the cylinder using a liquid injection device (HYM-JS-08 manufactured by Fuji Techno Industry Co., Ltd.) heated to 80 ° C. It was fed to the extruder from the position between the mouth. The liquid injection device was set to supply a constant amount, and the supply amounts of other raw materials were precisely measured with a measuring instrument [CWF manufactured by Kubota Corporation]. When it contained F-2 component (inorganic filler), it supplied so that it might become a predetermined | prescribed ratio using the side feeder from the 2nd supply port. Using a vent type twin screw extruder with a diameter of 30 mmφ [TEX30XSST, manufactured by Nippon Steel Works, Ltd.], it was melt-extruded and pelletized at a cylinder temperature of 250 ° C., a screw rotation speed of 200 rpm, a discharge rate of 20 kg / h, and a vent pressure reduction degree of 3 kPa. .

2. Preparation of molded product After the obtained pellets were dried at 80 ° C. for 5 hours in a hot air circulating dryer, the injection temperature was evaluated by a cylinder temperature of 250 ° C., a mold temperature of 40 ° C., and a molding cycle of 40 seconds. A test piece was prepared.

3. Evaluation method Each value in the examples was determined by the following method.

(1) Appearance The pellets after drying were used in an injection molding machine (Sumitomo Heavy Industries, Ltd .: ULTRA220-NIVA) having a cylinder inner diameter of 50 mmφ, and the casing molding of the notebook computer shown in FIG. Molding was performed at a mold temperature of 40 ° C. and a molding cycle of 40 sec. The appearance was evaluated using the obtained molded product. The case where an agglomerate-like material was seen was marked with ×, and the surface with a uniform surface was marked with ○.

(2) Hydrolysis resistance Using a pressure cooker (Hirayama Seisakusho cooker pc-305III / V), the test was conducted under specific processing conditions (processing temperature: 105 ° C., processing humidity: 100%, processing time: 4 hours). performed, using a Toyo Seiki Seisakusho SEMI AUTO mELT INDEXER 2A, 250 ℃ conforming to ISO1133 standard pellets after treatment, melt volume rate (MVR value, ^unit: cm 3 / 10min) in 2.16kg load was measured . On the other hand, the MVR value of the pellets before treatment was measured in the same manner. A value obtained by subtracting the MVR value before the treatment from the MVR value after the treatment was evaluated as ΔMVR. Such ΔMVR it is good hydrolysis resistance The ^smaller, less preferably 50 cm 3 / 10min.

(3) Heat resistance The deflection temperature under load was measured according to ISO75-1 and 75-2. The test piece was 80 mm long × 10 mm wide × 4 mm thick. Although the required deflection temperature differs depending on the application, it is preferably 100 ° C. or higher for a molded product not containing a flame retardant and 70 ° C. or higher for a molded product containing a flame retardant.

(4) 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 flame retardant).
Tables 1 and 2 show the evaluation results of the examples and comparative examples.

In addition, the raw material used by the Example and the comparative example is as follows.
(Component A: aromatic polycarbonate resin)
A: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 25,110 (Panlite L-1250WQ (trade name) manufactured by Teijin Chemicals Ltd.)
(B component: polylactic acid resin and / or copolymer of lactic acid and other hydroxycarboxylic acid)
B-1: NatureWorks Co. polylactic acid, grade name "NatureWorks4032D" (D-isomer content = 1.4%, MVR value ⁼ 2 cm 3 / 10min, water content = 360 ppm, Tm = 166 ° C., a weight average molecular weight = 220 , 000)
B-2: NatureWorks Co. polylactic acid, grade name "NatureWorks4060D" (D-isomer content = 12.0%, MVR value ⁼ 3 cm 3 / 10min, water content = 3,190Ppm, no Tm =, weight average molecular weight = 200,000)
(C component: phenoxy resin)
C-1: Phenoxy resin manufactured by Japan Epoxy Resin Co., Ltd., “jER1256” (weight average molecular weight 51,897, epoxy equivalent 8,300 g / eq)
(Other than C component)
C-2: Japan Epoxy Resin Co., Ltd. epoxy resin, “jER828” (weight average molecular weight 370, epoxy equivalent 186 g / eq)
C-3: Cresol novolak type epoxy resin manufactured by Toto Kasei Co., Ltd., “YDCN-704A” (epoxy equivalent 205 g / eq)
C-4: Glycidyl methacrylate manufactured by Mitsubishi Rayon Co., Ltd., “KP-7653” (weight average molecular weight 20,000, epoxy equivalent 170 g / eq)
(D component: antioxidant)
D-1: n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate (“Irganox” 1076 manufactured by Ciba Japan Co., Ltd.)
D-2: Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (“Adeka Stub” PEP-24G manufactured by Asahi Denka Kogyo Co., Ltd.)
(E component: flame retardant)
E: Phosphoric ester based on bisphenol A bis (diphenyl phosphate) manufactured by Daihachi Chemical Industry Co., Ltd., “CR-741”
(F component: inorganic filler)
F-1: Hayashi Kasei Kogyo Co., Ltd. talc, “HS-T0.8” (plate, average particle size 2 μm)
F-2: Glass fiber manufactured by Nittobo Co., Ltd., “3PE-937S” (diameter 13 μm, length 3 mm, converged by epoxy compound)
(Other ingredients)
i-1: Low molecular weight polyethylene “Hiwax 405MP” manufactured by Mitsui Chemicals, Inc.
i-2: Epoxy group-containing acrylic copolymer manufactured by NOF Corporation, “Modiper AT-14630”
i-3: Alkyl acrylate copolymer manufactured by Mitsubishi Rayon Co., Ltd., “methabrene P-530A” (weight average molecular weight 3.1 million)
i-4: Polytetrafluoroethylene-based mixture manufactured by Mitsubishi Rayon Co., Ltd., “Methbrene A-3750” (mixture made of polytetrafluoroethylene acrylic copolymer, polytetrafluoroethylene content 50% by weight))

  As is apparent from the results in Tables 1 and 2, the resin composition obtained by adding a phenoxy resin to a mixture of a polycarbonate resin and a polylactic acid resin has a good surface appearance, excellent hydrolysis resistance, and heat resistance. An excellent molded product can be obtained.

1 Molded product body imitating the laptop housing 2 Gate (2-point pin gate)

Claims (8)

  (A) 10 to 100 parts by weight of a copolymer (B component) of polylactic acid resin and / or lactic acid and other hydroxycarboxylic acid with respect to 100 parts by weight of aromatic polycarbonate resin (component A), and (C) A resin composition containing 0.001 to 10 parts by weight of a phenoxy resin (component C). Furthermore, the resin composition of Claim 1 which contains 0.01-2 weight part of (D) antioxidant (D component) with respect to 100 weight part of A component.   The resin composition according to claim 2, wherein the component D is at least one antioxidant selected from the group consisting of phosphite compounds, phosphonite compounds, hindered phenol compounds, and thioether compounds.   The resin composition of any one of Claims 1-3 which contains 0.1-100 weight part of (E) flame retardant (E component) with respect to 100 weight part of A component.   The resin composition of any one of Claims 1-4 which contains 0.1-100 weight part of (F) inorganic filler (F component) with respect to 100 weight part of A component.   The molded article which consists of a resin composition of any one of Claims 1-5.   The molded article according to claim 6, which is molded by at least one molding method selected from the group consisting of injection molding, extrusion molding, thermoforming, blow molding and foam molding.   The molded article according to claim 6 or 7, which is a part selected from the group consisting of automobile parts, electrical / electronic parts, electrical equipment exterior parts, and OA exterior parts.

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