JP5480687B2 - Aromatic polycarbonate resin composition with improved surface appearance - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition. More specifically, it is a resin composition containing a specific proportion of a polylactic acid resin and a compatibilizing agent that have a low environmental impact in an aromatic polycarbonate resin, has a low environmental impact, and is suitable for an aromatic polycarbonate resin / polylactic acid resin alloy. The present invention relates to an aromatic polycarbonate resin composition that has no uneven pearly luster and is excellent in surface appearance.

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. A representative example of biomass plastic is polylactic acid, which has relatively high heat resistance and mechanical properties among biomass plastics, so its application is expanding to tableware, packaging materials, general merchandise, etc. Sexuality has also been considered. It is known to blend a natural polymer such as corn starch with an aromatic polycarbonate resin (see Patent Document 1), a resin composition of polylactic acid and an aromatic polycarbonate resin, and the resin composition has a good pearly luster. It is also known to have excellent fluidity, heat resistance, rigidity and the like (see Patent Document 2). 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 transparency, and its brittleness is improved (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, the aromatic polycarbonate resin and the polylactic acid resin have poor compatibility, and no means for eliminating the uneven pearly luster produced on the surface of the molded product has been found so far.

JP 7-506863 A JP-A-7-109413 JP-A-11-140292 JP 2002-105298 A

  A first object of the present invention is to provide an aromatic polycarbonate resin composition having an improved surface appearance and having a reduced environmental load. The second object of the present invention is to obtain a resin composition excellent in strength and rigidity.

  As a result of intensive studies to achieve the above object, the present inventors have surprisingly found that a composition containing a specific ratio of an aromatic polycarbonate, a polylactic acid resin and a compatibilizer has a uniform and good surface appearance. The inventors have found that a resin composition that achieves the first object described above can be obtained. Furthermore, it succeeded in obtaining the outstanding intensity | strength and rigidity with respect to this composition. The present inventors have further studied based on such knowledge and completed the present invention.

  In order to solve the above-mentioned problems, the present inventors have intensively studied to complete the present invention. That is, the present inventors made (A) an aromatic polycarbonate resin (component A) 55 to 95% by weight and (B) a polylactic acid resin (component B) 5 to 45% by weight with respect to 100 parts by weight of a resin composition. And (C) an aromatic polycarbonate resin composition containing 0.1 to 30 parts by weight of a compatibilizing agent (component C) which consists essentially of an acrylic component and contains an epoxy group.

  The resin composition of the present invention is a resin composition comprising a specific ratio of an aromatic polycarbonate resin, polylactic acid and a compatibilizer, and has improved surface appearance, strength and rigidity, and in addition, has an environmental impact. It is to reduce. With such characteristics, the resin composition has an excellent surface appearance, and the molding thereof is excellent in strength and rigidity. Therefore, it is possible to provide a resin material with 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-phenylenediisopropyl Pyridene) 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.

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.

  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 a polycarbonate resin (A-3-1 component) having a viscosity average molecular weight of 7 × 10 ⁴ to 2 × 10 ^{6, and} a polycarbonate resin having a viscosity average molecular weight of 1 × 10 ^{4 to} 3 × 10 ⁴ Polycarbonate resin (A-3 component) consisting of (A-3-2 component) and having a viscosity average molecular weight of 1.6 × 10 ^{4 to} 3.5 × 10 ⁴ (hereinafter, “high molecular weight component-containing polycarbonate resin”) May also be used).

In such a high molecular weight component-containing polycarbonate resin (A-3 component), the molecular weight of the A-3-1 component is preferably 7 × 10 ^{4 to} 3 × 10 ⁵ , more preferably 8 × 10 ⁴ to 2 × 10 ⁵ , preferably ^{1 × 10 5 ~2 × 10 5} , particularly preferably ^{1 × 10 5 ~1.6 × 10 5} . The molecular weight of the A-3-2 component is preferably 1 × 10 ^{4 to} 2.5 × 10 ⁴ , more preferably 1.1 × 10 ^{4 to} 2.4 × 10 ⁴ , and still more preferably 1.2 × 10 ^4. to 2.4 × 10 ^4, particularly preferably ^{1.2 × 10 4 ~2.3 × 10 4} .

  The high molecular weight component-containing polycarbonate resin (component A-3) can be obtained by mixing the components A-3-1 and A-3-2 in various proportions and adjusting them so as to satisfy a predetermined molecular weight range. . Preferably, in 100% by weight of the A-3 component, the A-3-1 component is 2 to 40% by weight and the A-3-2 component is 60 to 98% by weight, more preferably the A-3-1 component is 5 to 20% by weight and the A-3-2 component is 80 to 95% by weight. Usually, the molecular weight distribution of the polycarbonate resin is in the range of 2-3. Therefore, it is preferable that the A-3-1 component and the A-3-2 component of the present invention satisfy the molecular weight distribution range. The molecular weight distribution is represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) calculated by GPC (gel permeation chromatography) measurement. And Mw is based on standard polystyrene conversion.

  In addition, as a method for preparing the A-3 component, (1) a method in which the A-3-1 component and the A-3-2 component 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 such a production method (production method of (2)), a separately produced A-3-1 component and / or Examples thereof include a method of mixing the A-3-2 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.

(B component: polylactic acid resin)
Usually, polylactic acid has higher melting point and crystallinity as the optical purity is higher. The melting point and crystallinity of polylactic acid are affected by the molecular weight and the catalyst used during polymerization. Usually, polylactic acid having an optical purity of 98% or higher has a melting point of about 170 ° C. and a relatively high crystallinity. Further, as the optical purity is lowered, the melting point and crystallinity are lowered. For example, polylactic acid having an optical purity of 88% has a melting point of about 145 ° C., and polylactic acid having an optical purity of 75% has a melting point of about 120 ° C. It is. Polylactic acid having an optical purity lower than 70% does not show a clear melting point and becomes amorphous.

  The weight average molecular weight of the polylactic acid resin used in the present invention is preferably 50,000 or more, more preferably 80,000 to 400,000, and still more preferably 100,000 to 300,000. By setting the weight average molecular weight of the polylactic acid resin to 50,000 or more, a film having excellent strength properties can be obtained when the polylactic acid resin is formed into a molded product such as a film.

  The polylactic acid of the present invention is synthesized by ring-opening polymerization from a cyclic dimer of lactic acid commonly called lactide, and the production method thereof is disclosed in USP 1,995,970, USP 2,362,511, USP 2,683,136. Yes. 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.

  The polylactic acid resin may be a copolymerized polylactic acid obtained by copolymerizing other monomer components having ester forming ability in addition to L-lactic acid and D-lactic acid. Examples of copolymerizable monomer components include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid, and other hydroxycarboxylic acids, as well as ethylene glycol, propylene glycol, and butane. Compounds containing a plurality of hydroxyl groups in the molecule such as diol, neopentyl glycol, polyethylene glycol, glycerin, pentaerythritol or their derivatives, succinic acid, adipic acid, sebacic acid, fumaric acid, terephthalic acid, isophthalic acid, 2 , 6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium sulfoisophthalic acid and the like, or compounds containing a plurality of carboxylic acid groups in the molecule. As a copolymerization component of the polylactic acid resin used in the present invention, it is preferable to select a biodegradable component.

  In the present invention, polylactic acid, which is a polymer containing only lactic acids, is preferably used, and poly L-lactic acid resin containing L-lactic acid as a main raw material is particularly preferable. Content of B component is 5-45 weight% in the total 100 weight% of A component and B component, 10-40 weight% is preferable and 20-30 weight% is more preferable. When the blending amount is less than 5% by weight, the fluidity and rigidity are not improved, and the appearance of the molded product surface is deteriorated and the strength is lowered. On the other hand, if it exceeds 45% by weight, the appearance of the molded product surface is deteriorated, the strength is lowered, and the heat resistance is lowered.

(C component: compatibilizer)
The resin composition of the present invention contains a compatibilizer as the C component. The compatibilizer in the present invention is one that promotes compatibilization with an aromatic polycarbonate resin and a polylactic acid resin, and has a function of finely dispersing the A component and the B component. Surface appearance and impact resistance can be obtained.

  Content of a compatibilizer is 0.1-30 weight part with respect to 100 weight part of resin components, Preferably it is 0.5-20 weight part, More preferably, it is 0.5-10 weight part. If it is less than 0.1 parts by weight, the effect as a compatibilizer is small, and if it exceeds 30 parts by weight, the surface appearance, heat resistance and mechanical properties are deteriorated, which is not preferable.

  Such a compatibilizing agent is a compatibilizing agent which consists essentially of an acrylic component and contains an epoxy group. The compatibilizer is preferably a compatibilizer comprising only an acrylic component represented by the following formulas (1) to (4) and containing an epoxy group. “Substantially composed of an acrylic component” means that the acrylic component is 95% by weight or more of the whole, and other components are included as long as it is less than 5% as long as the effect as a compatibilizer is not impaired. You can leave.

（式中Ｘは水素原子またはメチル基である。）

(In the formula, X is a hydrogen atom or a methyl group.)

The composition ratio of acrylic components (hereinafter simply referred to as (1) to (4)) represented by (1) to (4) constituting the C component of the present invention is the sum of (1) to (4). In 100 mol%, it is preferable that (1) is 40 to 60 mol%, (2) is 30 to 50 mol%, (3) is 1 to 15 mol%, (4) is 1 to 15 mol%, and (1) is 45. -55 mol%, (2) is 35-45 mol%, (3) is 1-10 mol%, (4) is more preferably 1-10 mol%, (1) is 50-55 mol%, (2) is It is particularly preferable that 35 to 40 mol%, (3) is 1 to 7 mol%, and (4) is 1 to 7 mol%. A compatibilizing agent composed essentially of an acrylic component and contained in such a range and containing an epoxy group exhibits excellent compatibility. Such a composition ratio can be calculated from a ¹³ C-NMR spectrum measured in a quantitative mode (reverse gate decoupled mode) using deuterated chloroform as a solvent.

X contained in the structural unit of the component C of the present invention is composed of a hydrogen atom and a methyl group, and a preferred ratio thereof is an acrylate when X is a hydrogen atom, and a methacrylate when X is a methyl group. In terms of a ratio, acrylate (X is hydrogen): methacrylate (X is a methyl group) = 30 to 60:70 to 40 is preferable, and acrylate: methacrylate = 35 to 55:65 to 45 is more preferable. It is particularly preferable that acrylate: methacrylate = 40 to 55:60 to 45. A compatibilizing agent consisting essentially of an acrylic component having such a ratio and containing an epoxy group exhibits excellent compatibility. The ratio of the acrylate and methacrylate can be calculated from a ¹³ C-NMR spectrum measured in a quantitative mode (reverse gate decoupled mode) using deuterated chloroform as a solvent.

  The weight average molecular weight of the component C of the present invention is not particularly limited, but is preferably 1,000 to 300,000, more preferably 5,000 to 250,000, and 7,000 to 200,000. More preferably. The weight average molecular weight here is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  Conventionally, as a compatibilizer, a graft copolymer having a polyethylene-based main chain and a vinyl-based polymer as a side chain (for example, polyethylene / glycidyl methacrylate, polyethylene / methyl acrylate / glycidyl methacrylate, poly (ethylene / glycidyl methacrylate)- g-polymethyl methacrylate), poly (ethylene / ethyl acrylate / maleic anhydride) -g-polymethyl methacrylate, poly (ethylene / ethyl acrylate / maleic anhydride) -g-poly (acrylonitrile / styrene), poly (methyl methacrylate) / Maleic anhydride)), poly (ethylene / methacrylic acid) and poly (ethylene / methacrylic acid) molecules crosslinked with metal ions, ionomer resins, styrene-butadiene block copolymers (for example, styrene -Styrene-butadiene block such as butadiene diblock copolymer, styrene-butadiene block copolymer such as styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS) A hydrogenated product of the copolymer) or an alkyl acrylate copolymer having a weight average molecular weight exceeding 1,000,000 has been used. However, these compatibilizers have little effect of compatibilizing the aromatic polycarbonate and the polylactic acid resin, and the surface has a non-uniform pearl luster and flow mark characteristic of the resin composition comprising the aromatic polycarbonate resin and the polylactic acid resin. It was difficult to achieve both the elimination of the problem and the improvement of the mechanical properties. On the other hand, a resin composition having a good surface appearance and excellent impact resistance can be obtained by using a compatibilizing agent which consists essentially of an acrylic component and contains an epoxy group. In order to prevent jetting, a small amount of the above-mentioned conventionally used compatibilizer may be added as long as the effect of adding the C component is not hindered. 0.5-5 weight part is preferable with respect to a part, More preferably, it is 0.5-3 weight part.

(D component: mold release agent)
The resin composition of the present invention may contain a release agent as the D component. The resin composition of the present invention often requires high dimensional accuracy. Therefore, the resin composition is preferably excellent in releasability. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound (poly And fluorine oil represented by fluoroalkyl ether), paraffin wax, and beeswax.
The content of component D is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the resin component.

(E component: antioxidant)
The resin composition of the present invention can contain an antioxidant as the E component. As the antioxidant, at least one kind of 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. As the phosphonite compound, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferable, and an antioxidant based on the phosphonite is Sandostab P-EPQ (trademark, manufactured by Clariant) and It is commercially available as Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) 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 component E is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 1 part by weight, and still more preferably 0.05 to 0.5 parts by weight with respect to 100 parts by weight of the resin component.
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, the hue, fluidity, and hydrolysis resistance of the molding process are improved. It is effective for improvement.

  In the resin composition of the present invention, other thermoplastic resins (for example, polyester, polyamide, polyacetal, modified polyphenylene ether, polyolefin resin, polyphenylene sulfide, etc.), flame retardant ( For example, brominated epoxy, brominated polystyrene, brominated polycarbonate, brominated polyacrylate, triphenyl phosphate, phosphate oligomer, phosphonic acid amide, silicone flame retardant, etc.), flame retardant aid (eg, sodium antimonate, trioxide) Antimony), anti-dripping agent (polytetrafluoroethylene having fibril-forming ability, etc.), nucleating agent (eg, sodium stearate, ethylene-sodium acrylate, etc.), impact modifier, UV absorber, light stabilizer, coloring Mixing agents It can be. Furthermore, in the present invention, various generally known fillers such as glass flake, wollastonite, kaolin clay, mica, and talc other than the fibrous inorganic reinforcing material can be used in combination according to the purpose of use.

(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 E 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.

  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 1-5, Comparative Examples 1-6]
1. Production of composition pellets Composition pellets were produced by the following method.
After the components shown in Table 1 and Table 2 were dry blended at the ratios shown in Table 1 and Table 2, a single-screw extruder with a diameter of 40 m / m and L / D = 32 (Isuzuka Koki Co., Ltd.) ): Made: Isuzu EXT40), melt-kneaded at a cylinder temperature of 250 ° C., extruded, and strand-cut to obtain pellets of each composition.

2. Preparation of molded product After the obtained pellets were dried at 80 ° C for 5 hours in a hot-air circulating dryer, test pieces for evaluation items were prepared by injection molding at a cylinder temperature of 250 ° C and a mold temperature of 40 ° C. did.

3. Evaluation method Each value in the examples was determined by the following method.
(1) Charpy impact strength Notched Charpy impact strength was measured according to ISO179. The test piece was 80 mm long × 10 mm wide × 4 mm thick. The Charpy impact strength needs to be ²⁰ KJ / m ² or more.
(2) Flexural modulus The flexural modulus was measured according to ISO178. The test piece was 80 mm long × 10 mm wide × 4 mm thick. The flexural modulus needs to be 1800 MPa.
(3) Appearance Using an injection molding machine (Sumitomo Heavy Industries, Ltd .: ULTRA220-NIVA) with a cylinder inner diameter of 50 mmφ for the pellets after drying, the casing molded product of the notebook computer shown in FIG. Molding was performed at a mold temperature of 40 ° C. and an injection speed of 30 to 75 mm / sec. The appearance was evaluated using the obtained molded product. A sample having a uniform appearance without pearly luster or a flow mark was marked with ◯.
(4) 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. The deflection temperature under load needs to be 70 ° C. or higher.
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)
B: NatureWorks Co., grade name "4032D" (D-isomer content ^{= 1.4%, MVR = 2cm 3} / 10min, water content = 360 ppm, Tm = 166 ° C., a weight average molecular weight = 220,000)
(C component: compatibilizer)
C-1: Epoxy group-containing acrylic copolymer (component ratio: (1) 52 mol%, (2) 37 mol%, (3) 6.8 mol%, (4) 4.2 mol%, molar ratio (acrylate / methacrylate) : 46.8 / 53.2, manufactured by NOF Corporation "Modiper" AT-14630)
C-2: ethylene / glycidyl methacrylate-g-poly (butyl acrylate / methyl methacrylate) (component ratio: polyethylene component 83.5 mol%, (1) 2.9 mol%, (3) 9.4 mol%, (4) 4 .2 mol%, molar ratio (acrylate / methacrylate) = 41.8 / 58.2, “Modiper” A-4300 manufactured by NOF Corporation
C-3: Hydrogenated styrene-butadiene-styrene copolymer (“Septon” 8006 manufactured by Kuraray Co., Ltd.)
(D component: mold release agent)
D: Low molecular weight polyethylene (“Hiwax” 405MP, manufactured by Mitsui Chemicals, Inc.)
(E component: antioxidant)
E-1: n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate (“Irganox” 1076 manufactured by Ciba Japan Co., Ltd.)
E-2: Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (“Adeka Stub” PEP-24G manufactured by Asahi Denka Kogyo Co., Ltd.)
(Other ingredients)
F-1: Alkyl acrylate copolymer (weight average molecular weight 3.1 million, manufactured by Mitsubishi Rayon Co., Ltd. “METABBRENE” P-530A)
The results are shown in Tables 1 and 2.

  As is clear from the results of Tables 1 and 2, in the resin composition in which the compatibilizing agent which is substantially composed only of the acrylic component and contains the epoxy group is added to the mixture of the polycarbonate resin and the polylactic acid resin, A molded product having a surface appearance and excellent impact resistance can be obtained.

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

Claims (4)

(C) 100 parts by weight of a resin component comprising an aromatic polycarbonate resin (component A) 55 to 95% by weight and (B) a polylactic acid resin (component B) 5 to 45% by weight, (C) the following formula (1) The aromatic polycarbonate resin composition which consists only of the acrylic component represented by-(4), and contains 0.1-30 weight part of compatibilizers (C component) containing an epoxy group.

(In the formula, X is a hydrogen atom or a methyl group.) The aromatic polycarbonate resin composition according to claim 1, further comprising 0.01 to 10 parts by weight of (D) a release agent (D component) with respect to 100 parts by weight of the resin component. The aromatic polycarbonate resin composition according to claim 1 or 2, further comprising 0.01 to 5 parts by weight of (E) an antioxidant (E component) with respect to 100 parts by weight of the resin component.   The aromatic polycarbonate resin composition according to any one of claims 1 to 3, wherein the component B is a poly L-lactic acid resin.

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