JP2010077349A - Resin composition and molded product made therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition forming sea-island structure that has a high degree of blackness and an excellent weld property; to provide a molded product useful for housing OA equipment or electric equipment obtained by multiple gate molding. <P>SOLUTION: The resin composition is obtained by blending 90 to 10 wt.% of a polylactic acid resin (A) and 10 to 90 wt.% of a branched aromatic polycarbonate resin (B), assuming that the total of (A) and (B) is 100 wt.%. The component (A) and the component (B) form the sea-island structure and the branched aromatic polycarbonate resin (B) is dispersed like islands. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is a resin composition forming a sea-island structure formed by blending (A) a polylactic acid resin and (B) a branched aromatic polycarbonate resin, a resin composition having excellent blackness and weld properties, and a molding comprising the same It is about goods.

  Polylactic acid resin is expected as a practically excellent biodegradable polymer because it has a high melting point and can be melt-molded. In addition, in the future, it is expected to be used as a general-purpose polymer made from bio raw materials, and various molded products are formed by injection molding, extrusion molding, and the like.

  However, the polylactic acid resin has a drawback that it is inferior in impact resistance and is brittle, and a modification has been desired.

  In addition, aromatic polycarbonate resins are excellent in transparency, impact resistance and mechanical properties, and are used for many purposes as transparent products and industrial products. It was.

  Patent Document 1 proposes blending polylactic acid as a method of modifying the fluidity of the aromatic polycarbonate resin. However, since the aromatic polycarbonate resin and polylactic acid are separated into individual phases to form a sea-sea structure, there is a problem that it is difficult to obtain a molded product having excellent blackness and is easily broken from the weld portion.

  Patent Document 2 proposes a method for improving the compatibility between a polylactic acid resin and a polycarbonate by melting and mixing a radical reaction initiator into the polylactic acid resin and the polycarbonate in a nitrogen atmosphere. There was a problem.

  Moreover, since the polylactic acid resin itself is easily combusted, it cannot be used for a member that needs to be flame retardant. On the other hand, aromatic polycarbonate resin is known as a material that is harder to burn than polylactic acid resin. However, since the polymer blend composition with polylactic acid resin is easily combusted, it cannot be used for a member that requires flame retardancy.

  In Patent Document 1 and Patent Document 2 described above, it is disclosed that a flame retardant can be blended with a polylactic acid resin or the like, but there is no disclosure about specific means for obtaining high flame retardancy.

Patent Document 3 discloses a resin composition in which an aromatic polycarbonate resin and a polylactic acid resin are blended with a polyorganosiloxane containing a nitrogen-containing organic group as a flame retardant. Patent Document 3 discloses that a branched aromatic polycarbonate resin is included as an aromatic polycarbonate, but there is no specific disclosure using a branched aromatic polycarbonate resin.
Japanese Patent No. 3279768 (page 1-2), (paragraph number [0008]) JP 2002-371172 A (page 1-2) JP 2008-37965 A (page 1-2), (paragraph number [0021])

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue.

  Therefore, the present invention is a resin composition that forms a sea-island structure, and aims to obtain a resin composition that is excellent in blackness and weld physical properties, and is useful for OA equipment or electrical equipment housings obtained by multipoint gate molding. It is an object to provide a simple molded product.

  The present inventors have found that a resin composition obtained by blending a polylactic acid resin and a branched aromatic polycarbonate resin has excellent characteristics that meet the above-mentioned purpose, and have reached the present invention.

That is, the present invention is as follows.
1. A resin composition comprising (A) 90 to 10% by weight of polylactic acid resin and (B) 10 to 90% by weight of branched aromatic polycarbonate resin, where the total amount of (A) and (B) is 100% by weight. A (A) component and a (B) component form a sea-island structure, and (B) a branched aromatic polycarbonate resin is dispersed in an island shape.
2. 100% by weight of the total amount of (A) and (B), and a resin composition 100 comprising (A) 90 to 10% by weight of a polylactic acid resin and (B) 10 to 90% by weight of a branched aromatic polycarbonate resin. A resin composition having a blackness of 25 or less when 1 part by weight of carbon black is blended with respect to parts by weight.
3. Further, 1 to 70 parts by weight of (C) thermoplastic resin other than the components (A) and (B) is blended with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) branched aromatic polycarbonate resin. The resin composition according to any one of 1 to 2.
4). 4. The resin composition according to 3, wherein the (C) thermoplastic resin is a vinyl resin.
5). Furthermore, (A) Polylactic acid resin (B) 1 to 4 formed by mix | blending 1-50 weight part of flame retardants with respect to 100 weight part of total amounts of branched aromatic polycarbonate resin. Resin composition.
6). 6. The resin composition according to 5, wherein the flame retardant (D) is at least one selected from a brominated flame retardant, a phosphorus flame retardant, a nitrogen compound flame retardant, a silicone flame retardant, and an inorganic flame retardant.
7.1 A molded article comprising the resin composition according to any one of 1 to 6.
The molded product according to 8.7, which is a housing of an OA device or an electrical device obtained by a multipoint gate.

  The present invention is a resin composition that forms a sea-island structure, and is excellent in blackness and weld physical properties when carbon black is blended, and the molded product of the present invention utilizes the above-mentioned properties to provide mechanical mechanism parts, It can be effectively used for various applications such as electronic parts, building members, automobile parts, and daily necessities, and in particular, a molded product useful for a housing of OA equipment or electric equipment obtained by multipoint gate molding can be provided.

  Hereinafter, the present invention will be described in detail.

  The (A) polylactic acid resin used in the present invention is a polymer mainly composed of L-lactic acid and / or D-lactic acid, but may contain other copolymerization components other than lactic acid. Other monomer units include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentane. Glycol compounds such as erythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid , Isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarbohydrate Acids, dicarboxylic acids such as 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid, hydroxycarboxylic acids such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, and caprolactone And lactones such as valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Such other copolymerization component is preferably 0 to 30 mol%, and preferably 0 to 10 mol%, based on all monomer components.

  In the present invention, it is preferable to use a polylactic acid resin (A) in which the optical purity of the lactic acid component is high from the viewpoint of compatibility. That is, (A) Of the total lactic acid components of the polylactic acid resin, it is preferable that the L-form is contained in 80% or more, or the D-form is contained in 80% or more, and the L-form is contained in 90% or more or the D-form is contained. It is particularly preferably 90% or more, more preferably 95% or more of L isomer or 95% or more of D isomer, 98% or more of L isomer, or 98% or more of D isomer. More preferably.

  It is also preferable to use a polylactic acid containing 80% or more of L-form and a polylactic acid containing 80% or more of D-form. It also contains 90% or more of polylactic acid containing 90% or more and L-form. It is more preferable to use polylactic acid in combination.

  (A) The polylactic acid resin may be modified, for example, by using maleic anhydride-modified polylactic acid resin, epoxy-modified polylactic acid resin, amine-modified polylactic acid resin, etc., not only heat resistance, It tends to improve mechanical properties, which is preferable.

  (A) As a manufacturing method of a polylactic acid resin, a well-known polymerization method can be used, and the direct polymerization method from lactic acid, the ring-opening polymerization method via a lactide, etc. can be mentioned.

  (A) The molecular weight or molecular weight distribution of the polylactic acid resin is not particularly limited as long as it can be substantially molded, but the weight average molecular weight is usually 10,000 or more, preferably 40,000 or more, Furthermore, it is desirable that it is 80,000 or more. The upper limit is preferably 350,000 or less from the viewpoint of fluidity during molding. The weight average molecular weight here refers to the molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography.

  (A) Although it does not restrict | limit especially about melting | fusing point of a polylactic acid resin, It is preferable that it is 120 degreeC or more, and also it is preferable that it is 150 degreeC or more. (A) Since the melting point of the polylactic acid resin tends to increase as the optical purity increases, the polylactic acid resin having a high melting point may be a polylactic acid resin having a high optical purity.

  The (B) branched aromatic polycarbonate resin in the present invention is an aromatic having no branched structure such as an aromatic homo or copolycarbonate obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. It is an aromatic polycarbonate resin containing an aromatic polycarbonate component having a branched nucleus structure derived from a branching agent by reacting the polycarbonate component with a branching agent, and the structure and production method thereof are described in JP-A-5-255578. Has been.

  The molecular weight of the branched aromatic polycarbonate resin is preferably a polymethyl methacrylate (PMMA) -converted weight average molecular weight in the range of 5000 to 500,000 as measured by gel permeation chromatography, and measured with a differential calorimeter. Those having a glass transition temperature in the range of 100 to 155 ° C are preferably used.

  Moreover, as long as the effects of the present invention are not impaired, the composition may contain one or more aromatic polycarbonate resins having no branched structure, aliphatic polycarbonate resins, aliphatic polyester carbonate resins, siloxane copolymer polycarbonate resins, and the like. .

  Examples of the aromatic dihydric phenol compound include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and bis (4- Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2 , 2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane or the like can be used, and these can be used alone or as a mixture.

  In addition, as the branching agent, a branching agent represented by the following general formula (I) is preferably used.

(R ^{1 to} R ⁷ in the formula may be the same or different and are each selected from hydrogen and an alkyl group having 1 to 5 carbon atoms.)

  Specific examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) -propane, 1,1,1-tris (4-hydroxyphenyl) -ethane, 1,1,1-tris (4- Hydroxyphenyl) -methane, 1,1,1-tris (3-methyl-4-hydroxyphenyl) -ethane, 1,1,1-tris (3-methyl-4-hydroxyphenyl) -methane, 1,1, 1-Tris (3,5-dimethyl-4-hydroxyphenyl) -ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) -methane, etc. can be used, and these can be used alone or as a mixture. In particular, 1,1,1-tris (4-hydroxyphenyl) -ethane and 1,1,1-tris (4-hydroxyphenyl) -methane are preferably used.

  The aromatic polycarbonate component having a branched nucleus structure derived from the branching agent is an aromatic polycarbonate having a branched nucleus structure as shown in FIG. 1 in which the aromatic polycarbonate component reacts with the hydroxyl terminal of the branching agent. Resin.

  Moreover, the ratio of the branching agent in the branched aromatic polycarbonate resin used in the present invention is based on the total amount of monomers constituting the aromatic polycarbonate resin from the viewpoint of blackness and weld properties when carbon black is blended. It is 0.05-2 mol%, 0.05-1.5 mol% is preferable and 0.05-1 mol% is more preferable.

  The resin composition of the present invention may contain one or more compounds such as hindered phenol-based, sulfur-based and phosphorus-based antioxidants.

  The blending amount of the component (A) and the component (B) is (A) polylactic acid from the viewpoint of a balance of injection moldability, heat resistance and toughness with respect to a total of 100% by weight of the component (A) and the component (B). 90 to 10% by weight of resin, (B) 10 to 90% by weight of branched aromatic polycarbonate resin, (A) 80 to 20% by weight of polylactic acid resin, and (B) 20 to 80% by weight of branched aromatic polycarbonate resin are preferable. (A) 75-25 weight% of polylactic acid resin, (B) 25-75 weight% of branched aromatic polycarbonate resin are more preferable.

  In the present invention, (A) a polylactic acid resin and (B) a branched aromatic polycarbonate resin are blended, so that (A) in the sea component using the polylactic acid resin as a matrix in the dispersion structure of the resin composition (B ) A sea-island structure can be formed in which branched aromatic polycarbonate resin is dispersed in islands. Here, the sea-island structure as referred to in the present invention refers to particles in which one resin component (A) is the main component (sea component) and the other resin component (B) is the main component (sea component). In the dispersion structure in which the island component is scattered, the dispersion shape of the island component (B) in the sea component (A) is dispersed in a spherical or elliptical shape, and the dispersed particle size is 20 μm in the case of a spherical dispersion. It is below, and 10 micrometers or less are preferable. In the case of an elliptical shape, the ratio of the long side to the short side is in the range of 1: 1 to 3: 1, the long side is 50 μm or less, preferably 30 μm or less, and having such a sea-island structure Thus, an excellent resin composition having specifically improved blackness and weld properties can be obtained. A typical example of such a sea-island structure obtained from the resin composition of the present invention is shown in FIG. In the drawing, the component (A) is white, the component (B) is indicated by black diagonal lines, and the component (A) may or may not be contained in the component (B).

  Such a sea-island structure resin composition can be obtained by kneading (A) a polylactic acid resin and (B) a branched aromatic polycarbonate resin with a melt kneader such as a twin screw extruder excellent in kneadability. At this time, you may mix | blend other components, such as (C) thermoplastic resin and (D) flame retardant other than (A) and (B) component.

  The dispersion structure when an aromatic polycarbonate resin having no branched structure is used instead of (A) the polylactic acid resin and (B) the branched aromatic polycarbonate resin of the present invention is as follows. In addition, an aromatic polycarbonate resin component that has an elliptical shape or streaks whose long side is three times longer than the short side and has no branching structure occupies a majority, and has a dispersed structure close to the sea-sea structure. In the present invention, it is expressed as a sea-sea structure and is handled as a structure different from the sea-island structure of the present invention, and a representative example is shown in FIG.

  As a method for observing the dispersion structure, for example, a sample cut from a pellet or an injection molded product can be observed with an optical microscope or a transmission electron microscope. For example, a sample cut from a cross section in the flow direction of a pellet is observed at a magnification of 500 times of a transmission electron microscope, and the observation site is photographed. The photograph shows white component (A) and (B) component or branched structure. The aromatic polycarbonate resin that does not have is identified as black, the dispersed shape is judged from the photograph, and the dispersed particle diameter can be easily measured from the scale of the photograph.

  In the present invention, by using a resin composition comprising (A) a polylactic acid resin and (B) a branched aromatic polycarbonate resin, for a total of 100 parts by weight of the component (A) and the component (B), When 1 part by weight of carbon black is blended, a molded product having a blackness of 25 or less can be obtained. Here, when the blackness of the molded product is 25 or less, it is a numerical value that is visually determined to be black, and the blackness is preferably 23 or less, more preferably 21 or less. In addition, the resin composition having a numerical value of blackness exceeding 25 exhibits a color closer to gray rather than black as the numerical value increases. When the blackness is 30, the resin composition is visually gray. It is a numerical value that is determined to be.

The carbon black is carbon black used as a conventional resin colorant. Examples of the carbon black include channel black, furnace black, acetylene black, anthracene black, oil smoke, pine smoke, and graphite. and the like, average particle size below 500 nm, carbon black dibutyl phthalate absorption 50~400cm ³ / 100g is preferably used, aluminum oxide treatment agent, silicon oxide, zinc oxide, zirconium oxide, polyol, silane coupling agents such as May be processed. Further, a black master obtained by mixing or melt-mixing one or more of the thermoplastic resins (C) other than the components (A), (B) or (A) and (B) of the present invention and the above carbon black is used. May be.

  As an example of producing a resin composition having a blackness of 25 or less, Furnace Black manufactured by Tegusa Japan Co., Ltd. with respect to 100 parts by weight of a resin composition comprising (A) a polylactic acid resin and (B) a branched aromatic polycarbonate resin. It can be obtained by blending 1 part by weight of “Printex” 35 and performing melt kneading using a twin screw extruder excellent in kneadability. At this time, you may mix | blend other components, such as (C) thermoplastic resin and (D) flame retardant other than (A) and (B) component.

  Next, the resin composition obtained by melt-kneading is injection-molded with an injection molding machine to produce a square plate (injection molded product) having a length of 80 mm × width of 80 mm × thickness of 3 mm. Measure.

The blackness is measured by using an SM color computer manufactured by Suga Test Instruments Co., Ltd., model SM-3, and measuring the L ^* value (lightness index) of the square plate according to Japanese Industrial Standard Z8722-1980. The value is defined as blackness. The L ^* value is the L ^* value (lightness index) of the L ^* a ^* b ^* color system recommended in 1976 by the International Lighting Commission (Commission Internationale 1 'Eclairage abbreviation CIE). The L ^* value (lightness index) is defined by Japanese Industrial Standard Z8105 (terms relating to color) and Japanese Industrial Standard Z8120 (optical terms), and is a coordinate in a three-dimensional color space having a perceptually almost uniform rate. This is an index that expresses brightness.

Further, handling the L ^* value (brightness index) as blackness is commonly used. For example, JFE Steel Corporation Technical Report No. 8 (June 2005) p. 83 is also used as blackness.

  In the present invention, thermoplastic resins other than the components (A) and (B) can be blended. (C) thermoplastic resins other than (A) and (B) components are vinyl resins, polyester resins other than component (A), phenoxy resins, cellulose ester resins, polyamide resins, polyolefin copolymers, polyethers Examples include imide resins, ionomer resins, polyphenylene ether resins, polyphenyl sulfide resins, phenol resins, and polyacetal resins. Vinyl resins, polyester resins other than component (A), cellulose ester resins, and polyamide resins are preferred, and vinyl resins. Is more preferably used.

  The blending amount of the (C) thermoplastic resin other than the components (A) and (B) is preferably 1 to 70 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B). 60 parts by weight is more preferable, 3 to 50 parts by weight is more preferable, and modification of one of blackness, weld physical properties, impact strength, heat resistance, and mechanical properties is recognized by mixing 1 part by weight, and 70 weights A good reforming effect can be obtained in any of the following characteristics: blackness, weld properties, impact strength, heat resistance and mechanical properties.

  The above-mentioned vinyl resin is one that further modifies blackness and weld physical properties by finely dispersing (A) polylactic acid resin and (B) branched aromatic polycarbonate resin and acting as a compatibilizer. , A resin obtained by polymerizing one or more monomers selected from aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid alkyl esters, and maleimide monomers with styrene or α-methylstyrene, or polybutadiene Examples include those obtained by graft polymerization of these monomers with rubber-based components such as rubber-based rubber, or those obtained by copolymerization (hereinafter, these may be collectively referred to as “copolymers”).

  Examples of the aromatic vinyl compound include vinyl toluene and divinylbenzene, examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and examples of the (meth) acrylic acid alkyl ester include methyl methacrylate. (Meth) acrylic acid alkyl esters such as ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and stearyl acrylate, and the like. N-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and derivatives thereof. Furthermore, the copolymer with the following component which can be copolymerized with vinyl resin is also contained in this invention. Specific examples of components capable of such copolymerization include diene compounds, maleic acid dialkyl esters, allyl alkyl ethers, unsaturated amino compounds, and vinyl alkyl ethers.

  Specific examples of vinyl resins include polystyrene resin (PS resin), polymethyl methacrylate resin (PMMA resin), methyl methacrylate / acrylonitrile / styrene resin, acrylonitrile / styrene resin (AS resin), styrene / butadiene resin, acrylate / Acrylonitrile / styrene resin (AAS resin), chlorinated polyethylene / acrylonitrile / styrene resin (ACS resin), acrylonitrile / ethylene / styrene resin (AES resin), styrene / N-phenylmaleimide resin, styrene / N-phenylmaleimide resin, styrene / Acrylonitrile / N-phenylmaleimide resin, styrene / methyl methacrylate / N-phenylmaleimide resin, acrylonitrile / butadiene / styrene resin (ABS resin), acrylonite Butadiene / methyl methacrylate / styrene resin (MABS resin), high impact polystyrene resin (HI-PS resin), styrene / butadiene / styrene resin (SBS resin), styrene / isoprene / styrene resin (SIS resin), styrene / Ethylene / propylene resin (SEP resin), styrene / ethylene / butylene / styrene resin (SEBS resin), etc., and these may be used as a mixture of two or more, and in particular, polymethyl methacrylate resin (PMMA resin) ), Acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / butadiene / methyl methacrylate / styrene resin (MABS resin), styrene / acrylonitrile / N-phenylmaleimide resin or styrene / methyl methacrylate A mixture of N-phenylmaleimide resin and acrylonitrile / butadiene / styrene resin (ABS resin), styrene / acrylonitrile / N-phenylmaleimide resin or styrene / methyl methacrylate / N-phenylmaleimide resin and acrylonitrile / butadiene / methyl methacrylate / A mixture with a styrene resin (MABS resin) or the like is preferably used (/ indicates copolymerization).

  In addition, acrylonitrile / butadiene / styrene resin (ABS resin) with a butadiene content of 30% or more, acrylonitrile / butadiene / methyl methacrylate / styrene resin (MABS resin), and styrene / ethylene / butylene / styrene resin (SEBS resin) have improved impact. It is particularly preferred because of its great effect.

  Further, it may be a vinyl resin obtained by graft polymerization or copolymerization of unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or epoxy group-containing vinyl monomers with the vinyl resin. Of these, vinyl resins obtained by graft polymerization or copolymerization of unsaturated acid anhydrides or epoxy group-containing vinyl monomers are preferable.

  Such epoxy group-containing vinyl monomers are compounds that share both radically polymerizable vinyl groups and epoxy groups in one molecule. Specific examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and itacon. Examples include glycidyl esters of unsaturated organic acids such as glycidyl acid, glycidyl ethers such as allyl glycidyl ether, and the above derivatives such as 2-methylglycidyl methacrylate. Among them, glycidyl acrylate and glycidyl methacrylate can be preferably used. These can be used alone or in combination of two or more. Of these, a styrene copolymer obtained by graft polymerization or copolymerization of glycidyl methacrylate is more preferably used.

  Unsaturated acid anhydrides are compounds that share both radically polymerizable vinyl groups and acid anhydrides in one molecule, and preferred examples include maleic anhydride.

  As a method for producing a vinyl resin obtained by graft polymerization or copolymerization of the unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated acid anhydride or epoxy group-containing vinyl monomer, a generally known method is adopted. A resin obtained by polymerizing styrene or α-methylstyrene with one or more monomers selected from aromatic vinyl compounds, vinyl cyanide compounds, alkyl (meth) acrylates, and maleimide monomers, and the like A method of copolymerizing other monomers copolymerizable with unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or epoxy group-containing vinyl monomers, the styrene copolymer In addition, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or epoxy group-containing vinyl monomers Body of and a method of graft polymerization. Such copolymerization and graft polymerization can also be performed by known methods.

  The amount used when graft polymerization or copolymerization of unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or epoxy group-containing vinyl monomers is the compatibility of component (A) and component (B). Although it is not particularly limited as long as it is effective to improve the viscosity, it is preferably 0.05% by weight or more based on the vinyl resin, and if it is copolymerized in a large amount, it tends to decrease fluidity or gelation. Yes, preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less.

  Further, it may be a vinyl resin obtained by epoxy-modifying the vinyl resin with an epoxidizing agent such as peroxides, performic acid, peracetic acid, and perbenzoic acid. In this case, it is preferable that a diene monomer is randomly copolymerized or block copolymerized with the vinyl resin in order to effectively perform the epoxy modification. As examples of diene monomers, butadiene, isoprene and the like are preferably used. Examples of suitable methods for producing these epoxy-modified vinyl resins are disclosed in JP-A-6-256417, JP-A-6-220124 and the like.

  In addition, the amount of epoxy group introduced into the vinyl resin in the epoxy group introducing method using an epoxidizing agent is not particularly limited as long as it is effective for improving the compatibility of the component (A) and the component (B). However, the epoxy equivalent is preferably 100 g / equivalent to 10,000 g / equivalent, more preferably 200 to 5000 g / equivalent, and still more preferably 250 to 3000 g / equivalent. The epoxy equivalent of these resins can be measured by the method described in JP-A-6-256417.

  Further, a multilayer structure in which a vinyl resin is used in any one of the multilayer structures including the innermost layer (core layer) and the outer layer (shell layer) covering the inner layer is also used as the vinyl resin of the present invention. Further, in the case of a multilayer structure having three or more layers, a vinyl resin may be used for the intermediate layer, and the multilayer structure can also be used as the vinyl resin of the present invention. The number of layers to be configured is composed of two or more layers.

  Preferred examples of the multilayer structure include those in which the core layer is a dimethylsiloxane / butyl acrylate polymer and the outermost layer is a vinyl resin, the core layer is a vinyl resin, and the outermost layer is dimethylsiloxane / acrylic acid. Examples thereof include butyl polymer, and any of the layers may be modified with glycidyl methacrylate or acid anhydride.

  The particle diameter of the multilayer structure is not particularly limited, but is preferably 0.01 μm or more and 1000 μm or less, more preferably 0.02 μm or more and 100 μm or less, and particularly Most preferably, it is 0.05 μm or more and 10 μm or less.

  In the multilayer structure, the weight ratio of the core layer to the outermost layer is not particularly limited, but the core layer is 10 parts by weight or more and 90 parts by weight or less with respect to the entire multilayer structure polymer. Furthermore, it is more preferable that it is 30 to 80 weight part.

  Moreover, as a multilayer structure, the commercial item which satisfy | fills above-described conditions may be used, and it can also produce and use by a well-known method.

  Commercially available multilayer structures include, for example, “Metablene” manufactured by Mitsubishi Rayon Co., Ltd., “Kane Ace” manufactured by Kaneka Chemical Industry Co., Ltd., “Paraloid” manufactured by Kureha Chemical Co., Ltd., “Acryloid” manufactured by Rohm and Haas Co., Ltd., Takeda Examples thereof include “STAPHYLOID” manufactured by Yakuhin Kogyo Co., Ltd. and “Parapet SA” manufactured by Kuraray Co., Ltd. These may be used alone or in combination of two or more, and may be used in combination with other vinyl resins.

  Further, it may be a resin containing a vinyl resin as a branched chain of the graft copolymer, and examples of the resin that becomes the main chain include polyolefin, acrylic resin, and polycarbonate resin. Any of the main chains may be modified with glycidyl methacrylate or acid anhydride. Specific examples include poly (ethylene / glycidyl methacrylate) -g-polymethyl methacrylate (E / GMA-g-PMMA). , Poly (ethylene / glycidyl methacrylate) -g-polystyrene (E / GMA-g-PS), poly (ethylene / glycidyl methacrylate) -g-AS (E / GMA-g-AS), etc. ("-g -"Represents a graft and"-/-"represents copolymerization).

  Moreover, as said commercial item, the Nippon Oil & Fats company "Modiper" etc. are mentioned, for example, You may use it individually or in mixture with another vinyl resin.

  The polyester resin is one or more selected from (i) dicarboxylic acids or ester-forming derivatives thereof and diols or ester-forming derivatives thereof, (b) hydroxycarboxylic acids or ester-forming derivatives thereof, and (c) lactones. Is a polymer or copolymer obtained by polycondensation of (A), a thermoplastic polyester resin other than polylactic acid resin.

  Preferred examples of the thermoplastic polyester resin other than the above (A) polylactic acid resin include polyethylene terephthalate, polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polyethylene (terephthalate / succinate), polybutylene. (Terephthalate / succinate), polyester elastomer, polypropylene terephthalate, polybutylene terephthalate / poly (tetramethylene oxide) glycol, polybutylene succinate, polycaprolactone and the like. Particularly preferred examples include polybutylene terephthalate and polypropylene terephthalate. , Polybutylene terephthalate, poly (tetramethylene oxide) glycol, poly Examples include at least one selected from tylene (terephthalate / succinate) and polybutylene succinate, which may be used alone or in combination of two or more, and contains a thermoplastic polyester resin. By doing so, it is possible to obtain a resin composition and a molded product in which any of moldability, heat resistance, and mechanical properties is improved.

  Examples of the cellulose ester resin include cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate phthalate. (A) Compatible or miscible with polylactic acid resin From the viewpoint, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate phthalate are preferable, and cellulose triacetate and cellulose acetate propionate are more preferable. Moreover, it is preferable that the substitution degree of the hydroxyl group in cellulose (average number of hydroxyl groups substituted by cellulose ester) is 0.5 to 2.9 per glucose unit. In addition, from the viewpoint of better compatibility or miscibility with (A) polylactic acid resin, the degree of substitution is preferably 1.5 to 2.9, and more preferably 2.0 to 2.8. More preferred. Moreover, said substitution degree can be calculated | required by using and esterifying the esterifying agent produced | generated by alkaline hydrolysis to a high performance liquid chromatography.

  The above cellulose ester resins may be used alone or in combination of two or more, and by blending the cellulose ester resin, the moldability, mechanical properties, and heat resistance of the resin composition of the present invention. A resin composition and a molded product obtained by modifying the above can be obtained.

  The polyamide resin is a thermoplastic polymer having an amide bond starting from amino acids, lactams or diamines and dicarboxylic acids, and the polyamide resins include nylon 6, nylon 66, nylon 11, nylon 12, nylon 6 / 10, nylon 6/12, nylon 11/6, and copolymers of these with polyethylene glycol, copolymer polyamide, mixed polyamide, polyamide elastomer, and the like. Nylon 6, nylon 11, nylon 12, nylon 6 / Polyethylene glycol and polyamide elastomer are more preferable, and nylon 6 and nylon 6 / polyethylene glycol are particularly preferable.

  The above polyamide resins may be used singly or in combination of two or more. By blending the polyamide resin, the moldability, mechanical properties and heat resistance of the resin composition of the present invention are improved. A refined resin composition and molded product can be obtained.

  In this invention, you may mix | blend (D) a flame retardant with a resin composition. The flame retardant (D) in the present invention is not particularly limited as long as it is a substance added for the purpose of imparting flame retardancy to the resin composition of the present invention. Examples include flame retardants, phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants, and other inorganic flame retardants, and at least one or more of these can be selected and used.

  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.

  The phosphorus-based flame retardant used in the present invention is not particularly limited, and generally used phosphorus-based flame retardants can be used. Typically, phosphoric esters, phosphazene compounds, and phosphorus-based phosphaphenanthrene skeletons Examples include flame retardants and organic phosphorus compounds such as polyphosphates and red phosphorus.

  Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate , Tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid Phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl- -Acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resorcinol polyphenyl Condensed phosphate esters such as phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, biphenyl polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate and condensates thereof; Can be mentioned. Examples of commercially available condensed phosphate esters include PX-200, PX-201, PX-202, CR-733S, CR-741, and CR747 manufactured by Daihachi Chemical Industry Co., Ltd.

  Moreover, the phosphate and polyphosphate which consist of a salt with phosphoric acid, polyphosphoric acid, a metal of group IA-IVB of the periodic table, ammonia, an aliphatic amine, and an aromatic amine can also be mentioned. As typical salts of polyphosphates, lithium salts, sodium salts, calcium salts, barium salts, iron (II) salts, iron (III) salts, aluminum salts and the like as metal salts, methylamine salts as aliphatic amine salts, There are ethylamine salt, diethylamine salt, triethylamine salt, ethylenediamine salt, piperazine salt, etc., and aromatic amine salts include pyridine salt, triazine salt, melamine salt, ammonium salt, especially nitrogen-containing phosphorus flame retardant and phosphine Acid metal salts are preferably used, and specific examples include melamine polyphosphate, melamine polymelamine with a melamine / melam / melem structure, ammonium polyphosphate and phosphinic acid metal salts (salt species include aluminum, calcium and zinc). The city of melamine polyphosphate that can be mentioned Ciba Geigy's “Merapua” 200, melamine, melam, and melem polyphosphate melamine commercially available as “Phosmel” PMP-200 manufactured by Nissan Chemical Industries, Ltd. “Exorit” (registered trademark) OP-1312 and OP-1240 manufactured by Clariant Japan can be mentioned as commercial examples.

  In addition to the above, halogen-containing phosphate esters such as trischloroethyl phosphate, trisdichloropropyl phosphate, tris (β-chloropropyl) phosphate), and a structure in which a phosphorus atom and a nitrogen atom are connected by a double bond. Phosphazene compounds, phosphoric ester amides, and phosphorus-based flame retardants having a phosphaphenanthrene skeleton. Commercially available phosphazene compounds include “RABITR” (registered trademark) FP-100, FOSMI PHARMACEUTICAL CO., LTD. As commercial products of phosphorus-based flame retardants with a faphenanthrene skeleton, BCA and M-Ester of Sanko Co., Ltd. can be mentioned as commercial examples.

  Further, as red phosphorus, not only untreated red phosphorus but also red phosphorus treated with one or more compound films selected from the group consisting of thermosetting resin coatings, metal hydroxide coatings, and metal plating coatings. It 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 coating is not particularly limited as long as it can coat 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 can coat 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.

  Examples of the nitrogen compound-based flame retardant used in the present invention include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amides, aromatic amides, urea, thiourea and the like. . In addition, nitrogen-containing phosphorus flame retardants such as ammonium polyphosphate as exemplified in the above phosphorus flame retardant are not included in the nitrogen compound flame retardant referred to herein. Examples of the aliphatic amine include ethylamine, butylamine, diethylamine, ethylenediamine, butylenediamine, triethylenetetramine, 1,2-diaminocyclohexane, 1,2-diaminocyclooctane and the like. Examples of the aromatic amine include aniline and phenylenediamine. Examples of nitrogen-containing heterocyclic compounds include uric acid, adenine, guanine, 2,6-diaminopurine, 2,4,6-triaminopyridine, and triazine compounds. Examples of the cyan compound include dicyandiamide. Examples of the aliphatic amide include N, N-dimethylacetamide. Examples of aromatic amides include N, N-diphenylacetamide.

  The triazine compounds exemplified above are nitrogen-containing heterocyclic compounds having a triazine skeleton, and are triazine, melamine, benzoguanamine, methylguanamine, cyanuric acid, melamine cyanurate, melamine isocyanurate, trimethyltriazine, triphenyltriazine, amelin, and amelide. And thiocyanuric acid, diaminomercaptotriazine, diaminomethyltriazine, diaminophenyltriazine, diaminoisopropoxytriazine and the like.

  As melamine cyanurate or melamine isocyanurate, an addition product of cyanuric acid or isocyanuric acid and a triazine compound is preferable, usually an addition having a composition of 1 to 1 (molar ratio) and optionally 1 to 2 (molar ratio). You can list things. Although it is produced by a known method, for example, a mixture of melamine and cyanuric acid or isocyanuric acid is made into a water slurry and mixed well to form both salts into fine particles, and then the slurry is filtered and dried. Later it is generally obtained in powder form. The salt does not need to be completely pure, and some unreacted melamine, cyanuric acid or isocyanuric acid may remain. Moreover, the average particle diameter before blending with the resin is preferably 100 to 0.01 μm, more preferably 80 to 1 μm from the viewpoint of flame retardancy, mechanical strength, and surface property of the molded product.

  Of the nitrogen compound-based flame retardants, nitrogen-containing heterocyclic compounds are preferable, among which triazine compounds are preferable, and melamine cyanurate is more preferable.

  When the dispersibility of the nitrogen compound flame retardant is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate or a known surface treatment agent such as polyvinyl alcohol or metal oxide may be used in combination. Good.

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.

  Other inorganic flame retardants used in the present invention include magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, tin oxide, oxidation Metal of tin salt, zinc sulfate, zinc oxide, ferrous oxide, ferric oxide, stannous oxide, stannic oxide, zinc borate, calcium borate, ammonium borate, ammonium octamolybdate, tungstic acid Examples thereof include salts, complex oxide acids of tungsten and metalloid, ammonium sulfamate, and swellable graphite. Of these, aluminum hydroxide, zinc borate, and swellable graphite are preferable.

  The (D) flame retardant may be used alone or in combination of two or more. In addition, when using aluminum hydroxide, it is preferable to knead (A) polylactic acid resin and (B) branched aromatic polycarbonate resin in advance, and melt and mix them at a kneading temperature of 210 ° C. It is preferable to use aluminum hydroxide.

  Among the flame retardants (D), at least one or a combination of two or more selected from phosphorus-based flame retardants containing no halogen, nitrogen compound-based flame retardants, silicone-based flame retardants, and other inorganic flame retardants Are preferably used. In the above, when two or more flame retardants are used in combination, it is preferable to use a phosphorus-based flame retardant together with another flame retardant. The nitrogen compound-based flame retardant used in combination with the phosphorus-based flame retardant is preferably a nitrogen-containing heterocyclic compound, more preferably a triazine compound, and further preferably melamine cyanurate. Moreover, as a silicone type flame retardant used together with a phosphorus type flame retardant, a silicone resin is preferable. Moreover, as other inorganic flame retardants used in combination with phosphorus flame retardants, aluminum hydroxide, zinc borate and swellable graphite are preferable. Further, the blending ratio with the phosphorus-based flame retardant can be combined with any amount, and the amount of the phosphorus-based flame retardant in 100% by weight of the flame retardant is particularly preferably 5% by weight or more, and 5 to 95% by weight. It is more preferable that

  (D) The flame retardant content is preferably 1 to 50 parts by weight, more preferably 2 to 45 parts by weight, with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) branched aromatic polycarbonate resin. 3 parts by weight to 40 parts by weight is particularly preferable. (D) A flame retardant effect is obtained by blending 1 part by weight or more of the flame retardant, and good flame retardancy is obtained by blending 50 parts by weight or less.

  In the present invention, (E) a fluorine resin can be further blended. The (E) fluorine-based resin in the present invention is a resin containing fluorine in a substance molecule, and exhibits a dripping prevention effect (dripping) during combustion, thereby shortening the combustion time. (E) Specific examples of the fluororesin include polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene. Copolymer, hexafluoropropylene / propylene copolymer, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymer, and the like. Among them, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, Tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, and polyvinylidene fluoride are preferred, especially polytetrafluoroethylene Tetrafluoroethylene / ethylene copolymer is preferred, and polytetrafluoroethylene is preferred, polytetrafluoroethylene-containing mixed powder comprising a polytetrafluoroethylene particles and an organic polymer is also preferably used. The molecular weight of the fluororesin such as polytetrafluoroethylene is preferably in the range of 100,000 to 10,000,000, more preferably in the range of 100,000 to 1,000,000, particularly for the extrudability and flame retardancy of the present invention. effective. Commercially available products of polytetrafluoroethylene include “Teflon” (registered trademark) 6-J, 6C-J, 62-J of Mitsui DuPont Fluorochemical Co., Ltd., “Fluon” of Asahi IC Fluoropolymers Co., Ltd. CD1 and CD076 are commercially available. Moreover, as a commercial item of the polytetrafluoroethylene containing mixed powder which consists of polytetrafluoroethylene particle | grains and an organic polymer, Mitsubishi Rayon Co., Ltd. "metabrene" (trademark) A-3000, A-3800. Are commercially available.

  In addition, polytetrafluoroethylene “Teflon” (registered trademark) 6-J and the like are prone to agglomerate, and when strongly mechanically mixed with other resin compositions using a Henschel mixer or the like, agglomeration may occur due to aggregation. There are problems in handling and dispersibility depending on conditions. On the other hand, a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is excellent in handling properties and dispersibility, and is particularly preferably used. The polytetrafluoroethylene-containing mixed powder composed of the polytetrafluoroethylene particles and the organic polymer is not limited, but polytetrafluoroethylene disclosed in Japanese Patent Application Laid-Open No. 2000-226523. Polytetrafluoroethylene-containing mixed powder composed of particles and an organic polymer, and the like. Examples of the organic polymer include aromatic vinyl monomers, acrylate monomers, and vinyl cyanide. An organic polymer containing 10% by weight or more of a monomer, and a mixture thereof may be used. The content of polytetrafluoroethylene in the polytetrafluoroethylene-containing mixed powder is from 0.1% by weight to 90%. It is preferable that it is weight%.

  The blending amount of the (E) fluorine-based resin is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) branched aromatic polycarbonate resin. 02 to 2 parts by weight is more preferable, 0.03 to 1 part by weight is more preferable, and the blending of 0.01 part by weight or more has an effect of improving the flame retardancy, and the effect of improving the flame retardancy is good at 3 parts by weight or less. Is obtained.

  In the present invention, for the purpose of modifying the durability performance of the resin composition of the present invention, such as heat resistance, hydrolyzability and wet heat resistance, further, an oxazoline compound, an oxazine compound, a carbodiimide compound, a carbodiimide-modified isocyanate compound, An epoxy compound and an isocyanate compound can be blended, and one kind or two or more kinds may be used.

  The compounding amount of the compound for modifying the durability is 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) branched aromatic polycarbonate resin. Yes, 0.2 parts by weight to 9 parts by weight is preferable, 0.3 parts by weight to 8 parts by weight is more preferable, and durability characteristics are improved by blending 0.1 parts by weight or more, and good at 10 parts by weight or less. Durability characteristics are obtained.

  The oxazoline compound is a compound having at least one oxazoline ring in the molecule, and examples of the oxazoline compound include 2,2′-m-phenylenebis (2-oxazoline), 2,2′-p-phenylenebis. (2-oxazoline) and the like, and a polymer compound obtained by grafting or copolymerizing an oxazoline compound can also be preferably used. Specific examples include a bisoxazoline / styrene / maleic anhydride copolymer, and a bisoxazoline / maleic anhydride. Examples include acid-modified polyethylene and bisoxazoline / maleic anhydride-modified polypropylene. Furthermore, it may be a mixture of the above oxazoline compound and / or a polymer compound grafted or copolymerized with the oxazoline compound and a thermoplastic resin, or may be used alone or in combination.

  The oxazine compound is a compound having at least one oxazine ring in the molecule, and as the oxazine compound, 2,2′-naphthylenebis (5,6-dihydro-4H-1,3-oxazine), 2, 2′-P, P′-diphenylenebis (5,6-dihydro-4H-1,3-oxazine) and the like, and a polymer compound obtained by grafting or copolymerizing an oxazine compound can also be preferably used. Examples include oxazine / styrene / maleic anhydride copolymer, oxazine / maleic anhydride modified polyethylene, oxazine / maleic anhydride modified polypropylene, and the like. Further, it may be a mixture of a polymer compound grafted or copolymerized with the above oxazine compound and / or oxazodine compound and a thermoplastic resin, or may be used singly or in combination.

  The carbodiimide compound is a compound having at least one carbodiimide group represented by (—N═C═N—) in the molecule. For example, the organic isocyanate is heated in the presence of a suitable catalyst to remove it. The carbodiimide compound can be produced by a carbonic acid reaction, and examples of the carbodiimide compound include N, N′-di-2,6-diisopropylphenylcarbodiimide, 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide, and carbodiimide compound and thermoplasticity. There may be a mixture with a resin, a mixture reacting with a carbodiimide compound and the end of a thermoplastic resin, or one or more of them may be used. Furthermore, it may be a carbodiimide-modified isocyanate compound that is a mixture of the above-described carbodiimide compound and an isocyanate compound, or a composite of a carbodiimide compound and an isocyanate compound, and may be used alone or in combination.

  The isocyanate compound is a compound represented by at least one (—NHCOO—) in the molecule and having an isocyanate group, and examples thereof include methylene diisocyanate and tolylene diisocyanate. A polyester or polyester is copolymerized with the isocyanate compound. Polyurethane resin may be used, or one or more may be used.

  The epoxy compound may be a monofunctional epoxy compound or a bifunctional or higher functional epoxy compound, but is preferably an epoxy compound having a glycidyl group, such as a glycidyl ester compound, a glycidyl ether compound, And glycidyl ester ether compounds. One or more of these epoxy compounds can be used.

  In addition, about the high molecular compound which grafted or copolymerized the glycidyl compound contained in (C) component, it is not contained in an epoxy compound here.

  Examples of the glycidyl ester compound include, but are not limited to, benzoic acid glycidyl ester, tBu-benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, pelargonic acid glycidyl ester, Steric acid glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, behenic acid glycidyl ester, versatic acid glycidyl ester, oleic acid glycidyl ester, linoleic acid glycidyl ester, linolenic acid glycidyl ester, behenolic acid glycidyl ester, stearol acid glycidyl ester Terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, Phthalenedicarboxylic acid diglycidyl ester, bibenzoic acid diglycidyl ester, methylterephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, Examples include succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetraglycidyl ester, and the like. More than seeds can be used.

  The glycidyl ether compound is not limited, but specific examples include phenyl glycidyl ether, p-phenylphenyl glycidyl ether, 1,4-bis (β, γ-epoxypropoxy). ) Butane, 1,6-bis (β, γ-epoxypropoxy) hexane, 1,4-bis (β, γ-epoxypropoxy) benzene, 1- (β, γ-epoxypropoxy) -2-ethoxyethane, 1 Others such as-(β, γ-epoxypropoxy) -2-benzyloxyethane, 2,2-bis- [р- (β, γ-epoxypropoxy) phenyl] propane and bis- (4-hydroxyphenyl) methane Examples include diglycidyl ether obtained by the reaction of bisphenol and epichlorohydrin. These may be used alone or in combination. Can.

  The epoxy compound that is preferably used is an epoxy compound in which a monofunctional glycidyl ester compound and a glycidyl ether compound are used in combination or a monofunctional glycidyl ester compound, and more preferably, the viscosity of the composition from which a monofunctional glycidyl ester compound is obtained. Excellent balance between stability and hydrolysis resistance.

  Moreover, in this invention, an inorganic filler can be further mix | blended and there exists an effect which improves electrical characteristics, such as a molded article whiteness of a resin composition, arc resistance, and tracking resistance. Examples of the inorganic filler include plate-like, granular and needle-like ones.

  As the plate-like and granular inorganic fillers, those obtained by pulverizing silicate minerals, silicate minerals and various minerals by processing such as pulverization are preferably used. Specific examples include bentonite, dolomite, barlite, fine silicate, aluminum silicate, silicon oxide, dosonite, shirasu balloon, clay, sericite, feldspar powder, zeolite (including synthetic zeolite), talc, mica, calcium carbonate , Glass flakes, glass beads, hydrotalcite and silica, etc., and talc and silica are preferably used because of the high whiteness of the resulting molded product, and the average particle size of the plate-like and granular inorganic fillers is 10 μm or less The decrease in mechanical properties is small, and more preferably 5 μm or less. The lower limit is preferably an average particle size of 0.5 μm or more, more preferably an average particle size of 1 μm or more from the viewpoint of handling properties during production. The average particle diameter is measured by a 50% cumulative distribution average particle diameter measured by a laser diffraction scattering method.

  Examples of the acicular inorganic filler include wollastonite (including synthetic wollastonite), kaolin, acicular calcium carbonate and the like, and acicular inorganic having an aspect ratio (average length / average diameter) of 3 to 20. A filler is preferable, and the average diameter is preferably 10 μm or less, and the deterioration of mechanical properties is small. More preferably, the average diameter is 5 μm or less.

  The compounding amount of the plate-like, granular and acicular inorganic fillers is 0.5 to 50 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) branched aromatic polycarbonate resin. 0.7 parts by weight to 40 parts by weight is preferable, 1 part by weight to 30 parts by weight is more preferable, electrical characteristics can be improved by blending 0.5 parts by weight or more, and blending by 50 parts by weight or less is good. Excellent electrical characteristics.

  Moreover, in this invention, a fibrous reinforcement can be mix | blended and what is normally used for reinforcement | strengthening of a thermoplastic resin can be used as a fibrous reinforcement. Specifically, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, sepiolite, asbestos, slag fiber, zonolite, elestite, plaster Fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber and other inorganic fibrous reinforcements, polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, kenaf, ramie Organic fibrous reinforcements such as cotton, jute, hemp, sisal, flax, linen, silk, Manila hemp, sugar cane, wood pulp, paper waste, waste paper and wool Among these fiber reinforcements, inorganic fibrous reinforcement is preferred Especially fiberglass and C aluminum whisker are preferred. Moreover, use of an organic fibrous reinforcing material is also preferable, and natural fibers and regenerated fibers are more preferable from the viewpoint of taking advantage of the biodegradability of the polylactic acid resin, and kenaf is particularly preferable.

  Moreover, the compounding quantity of a fiber reinforcement is 1 weight part-100 weight part with respect to 100 weight part of total amounts of (A) polylactic acid resin and (B) branched aromatic polycarbonate resin, and 2 weight part-80 weight part. Part by weight, more preferably 3 parts by weight to 60 parts by weight, more preferably 1 part by weight or more of the rigidity can be modified, and 100 parts by weight or less of the blend can provide good rigidity.

  The inorganic filler or fibrous reinforcing material may be coated or focused with a thermoplastic resin such as ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, such as aminosilane or epoxysilane. It may be treated with a coupling agent.

  In the present invention, a plasticizer can be further blended, and as the plasticizer, known ones generally used as polymer plasticizers can be used without particular limitation. For example, polyester plasticizer, glycerin plasticizer Benzoic acid of aliphatic polyol such as polycarboxylic acid ester plasticizer, polyalkylene glycol plasticizer, epoxy plasticizer, neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate Esters, fatty acid amides such as stearamide, aliphatic carboxylic esters such as butyl oleate, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, polyacrylic acid esters and paraffins And the like.

  Moreover, the compounding quantity of a plasticizer is 0.1-30 weight part with respect to 100 weight part of total amounts of (A) polylactic acid resin and (B) branched aromatic polycarbonate resin, 0.2-20 weight Part is preferable, and the range of 0.3 to 10 parts by weight is particularly preferable.

  In the present invention, it is preferable to add a plasticizer because moldability and heat resistance are improved.

  In the present invention, a crystal nucleating agent can be further blended. Examples of the crystal nucleating agent include known inorganic nucleating agents such as nitrides, organic nucleating agents such as organic carboxylic acid metal salts, carbon black, and titanium oxide. , Petals such as petals and ultramarine, sorbitols, and (A) a polymer nucleating agent having a melting point higher than that of polylactic acid resin, and the like may be used alone or in combination of two or more.

  The blending amount of the crystal nucleating agent is preferably 0.01 to 30 parts by weight, and 0.05 to 20 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin. Part is more preferable, and 0.1 to 10 parts by weight is particularly preferable.

  In the present invention, it is preferable to add a crystal nucleating agent because moldability and heat resistance are improved.

  In the present invention, the plasticizer and the crystal nucleating agent may each be used alone, but it is preferable from the viewpoint of moldability to use both in combination.

  In the present invention, a layered silicate can be further blended, and the formability can be improved. The layered silicate is more preferably blended with a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions. In the present invention, the layered silicate in which the exchangeable cation existing between the layers is exchanged with the organic onium ion is the exchange of the exchangeable cation of the layered silicate having the exchangeable cation between the layers with the organic onium ion. Inclusion compound.

  A layered silicate having an exchangeable cation between layers has a structure in which plate-like materials having a width of 0.05 to 0.5 μm and a thickness of 6 to 15 angstroms are laminated. Has a cation. The cation exchange capacity is 0.2 to 3 meq / g, and preferably the cation exchange capacity is 0.8 to 1.5 meq / g.

  Specific examples of layered silicates include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, and titanium phosphate. Examples thereof include swelling mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, and the like, which may be natural or synthesized. Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferable.

  In the present invention, the amount of layered silicate is preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) branched aromatic polycarbonate resin. -30 parts by weight is more preferable, and 1-20 parts by weight is particularly preferable.

  In the present invention, in addition to the carbon black used for the blackness, the resin is adjusted to various colors by blending at least one of titanium oxide, petal, ultramarine blue, calcined yellow, and pigments and dyes of various colors. It is also possible to improve the color, weather resistance (light) resistance, and conductivity. The blending amount of the pigment or dye is 100 parts by weight of the total amount of (A) polylactic acid resin and (B) branched aromatic polycarbonate resin. On the other hand, it is 0.01-10 weight part, Preferably it is 0.02-9 weight part, More preferably, it is 0.03-8 weight part.

  Further, as the titanium oxide, titanium oxide having a rutile form or anatase form and having an average particle diameter of 5 μm or less is preferably used, and aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, It may be treated with a polyol, a silane coupling agent or the like. In addition, the above-mentioned carbon black, titanium oxide, and various color pigments and dyes are melt blended with various thermoplastic resins in order to improve dispersibility with the resin composition of the present invention and to improve handling during production. Alternatively, it may be used as a blended mixed material. Particularly, the thermoplastic resin is preferably a thermoplastic resin of component (A), (B) or (C), and (A) polylactic acid resin is particularly preferably used.

  For the resin composition of the present invention, a stabilizer (hindered phenol-based antioxidant, phosphorus-based antioxidant, amine-based antioxidant, sulfur-based antioxidant, as long as the object of the present invention is not impaired. Light stabilizers, UV absorbers, copper damage inhibitors, etc.), mold release agents (fatty acids, fatty acid metal salts, oxy fatty acids, fatty acid esters, aliphatic partial saponified esters, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, Aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, modified silicone) and the like can be added as necessary.

  Although it does not specifically limit about the manufacturing method of the resin composition of this invention, For example, other than (A) polylactic acid resin, (B) branched aromatic polycarbonate resin, and (A) and (B) component as needed (C) Thermoplastic resin, (D) Flame retardant, (E) Fluorine resin, carbon black and other additives are blended in advance, and (A) in the range above the melting point of polylactic acid resin, uniaxial or 2 It is manufactured by a method of uniformly melting and kneading using a shaft extruder.

  The resin composition of the present invention is a composition having unique characteristics, and various methods are employed by methods such as extrusion molding, injection molding, blow molding, and spinning into various fibers such as undrawn yarn, drawn yarn, and superdrawn yarn. It can be processed into a product shape and used, and in particular, it can be used as a molded product for various uses such as mechanical mechanism parts, electrical / electronic parts, automobile parts, optical equipment, building members, and daily necessities. In particular, since the resin composition of the present invention is excellent in blackness and weld properties, it is a molded product used for a housing of OA equipment or electrical equipment obtained by a multipoint gate.

  Examples of the extrusion-molded product obtained by the above-described extrusion molding include extrusion-molded products such as films, inflation films, sheets, tubes and round bars, and can be used after being stretched. Further, it can be further processed into a molded product for various uses such as electric / electronic parts, automobile parts, optical equipment, building materials and daily necessities. In addition, examples of the mechanical mechanism parts of injection molded products obtained by injection molding include various types of bearings such as cleaning jigs, oilless bearings, stern bearings, underwater bearings, motor parts, lighters, typewriters, etc. As electrical and electronic parts for injection molded products, housings for electrical equipment, housings for OA equipment such as printers, personal computers, notebook computers, copiers, telephones, various covers and housings, various gears, various cases, sensors , LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, breakers, plugs, printed wiring boards, tuners, speakers, microphones, Headphone, small motor, magnetic head base, power module, semiconductor , LCD, FDD carriage, FDD chassis, motor brush holder, parabolic antenna, CD tray, cartridge, cassette, sorter, AC adapter, charging stand, switchboard, outlet cover, VTR parts, TV parts, iron, hair dryer, rice cooker parts , Microwave oven parts, acoustic parts, audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, office computer related parts, telephone related parts, mobile phone related parts, facsimile related parts, Examples of molding parts and casings that make up part or more of copier-related parts can be listed. Automotive parts for injection-molded parts include precision machine-related parts, alternator terminals, and alternator connectors. , IC regulators, various valves such as exhaust gas valves, fuel-related / exhaust / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling Water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane , Wiper motor related parts, dust distributor, starter switch, starter relay, transmission Wire harness, window washer nozzle, air conditioner panel switch board, coil for fuel-related electromagnetic valve, connector for fuse, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, A molded product that constitutes at least a part of an engine oil filter, an ignition device case, etc., and an optical instrument of an injection molded product may be a molded product that constitutes at least a part of a microscope, binoculars, camera, watch, etc. Can do. In addition, blow molded products are molded into the necessary shape as bellows, boots, bottles, and different diameter pipes / cylinders, such as mechanical mechanism parts, electrical / electronic parts, automobile parts, optical equipment, building components, and daily necessities. It can be used for various purposes as a molded product.

  Here, the multi-point gate will be described. In the injection mold used for the housing of OA equipment or electrical equipment, when the gate for guiding the molten resin into the mold is a single-point gate, the resin composition is uniformly filled. There is a problem that burrs are likely to occur because it is difficult and high molding pressure is required, and in order to solve the problem, the molten resin is often introduced into the mold using two or more multi-point gates. However, in the case of a multi-point gate mold, there is a problem that a weld portion where the molten resin and the molten resin intersect with each other is generated, and the portion is easily broken.

  Since the resin composition of the present invention is excellent in the above-mentioned weld physical properties, it is useful for molded products used for housings of OA equipment or electrical equipment obtained by a multipoint gate.

  The present invention will be described in more detail below by way of examples, but these examples do not limit the present invention.

[Measurement method for each characteristic]
In the examples and comparative examples, the characteristics were evaluated by the measurement methods described below.

1. (A) Component and (B) Component or Determination Method of Dispersion Structure of Polycarbonate Resin A sample of a transmission electron microscope is cut from the flow direction of the pellet, and the dispersion structure is observed at a magnification of 500 times of the transmission electron microscope. The observation site is photographed and the (A) component is identified as white, and the (B) component or polycarbonate resin is identified as black. In addition, the dispersion shape of the component (B) or the polycarbonate resin island component in the sea component (A) is roughly classified into spherical, elliptical, and streak dispersion. Spherical dispersion of 20 μm or less, ratio of long side to short side is 1: 1 to 3: 1, and material having an elliptical dispersion structure with long side of 50 μm or less is determined as sea-island structure, and phase structure is determined. Was marked as ○. The dispersed particle diameter was obtained from the scale of the photograph.

  A resin composition not defined in the sea-island structure and a shape in which the ratio of the long side to the short side exceeds 3: 1 is determined as streak dispersion, and the resin composition occupies a majority of the streaks dispersed component. Was determined to be a dispersed structure close to the sea-sea structure, and the phase structure was evaluated as x.

2. Blackness Using a Toshiba Machine IS55EPN injection molding machine, a square plate having a length of 80 mm, a length of 80 mm, and a thickness of 3 mm was obtained under the conditions of a molding temperature of 250 ° C. and a mold temperature of 50 ° C. Next, using a SM color computer manufactured by Suga Test Instruments Co., Ltd., model SM-3, the L ^* value (lightness index) of the square plate obtained by injection molding was measured according to Japanese Industrial Standard Z8722-1980, The value was defined as blackness. When the blackness is 25 or less, it is a numerical value that is visually determined to be black, and when the blackness is 30, it is a numerical value that is visually determined to be gray. .

3. Weld properties Using a Toshiba Machine IS55EPN injection molding machine, the molding conditions were a molding temperature of 250 ° C., a mold temperature of 50 ° C., injection time and holding time of 10 seconds, and cooling cycle time of 10 seconds. An ASTM No. 1 dumbbell having a thickness of 8 inches (about 3.2 mm) was obtained. The mold used for injection molding is molded with a two-point gate mold with gates on the left and right in the longitudinal direction of the dumbbell. The molten resin flowing from the left and right intersects at the center of the dumbbell and the weld part is The resulting mold was used.

  Subsequently, the obtained dumbbell was subjected to a tensile physical property test according to ASTM method D638, and the tensile strength was defined as weld strength and the tensile elongation at break was defined as weld elongation. The value was the average of three measured values.

4). Impact strength Using an IS55EPN injection molding machine manufactured by Toshiba Machine, a 1/8 inch (about 3.2 mm) thick Izod impact test piece with a molding temperature of 250 ° C. and a mold temperature of 50 ° C. was produced. According to ASTM D256, Izod impact strength with V notch was measured. The value of impact strength was an average value of seven measured values.

5). Flame retardancy Using a Toshiba Machine IS55EPN injection molding machine, a combustion test piece having a thickness of 1/16 inch (about 1.59 mm) was obtained under conditions of a molding temperature of 250 ° C and a mold temperature of 50 ° C. Next, a combustion test is performed in accordance with the vertical combustion test method of the American UL standard subject 94 (UL94), flame retardancy is evaluated, and the evaluation rank is V-0, V-1, V in order of excellent flame retardancy. -2 and those that did not correspond to the above rank were out of specification.

6). Hydrolyzability Seven Izod impact test pieces with V-notches as described in the above item 4 were put into a constant temperature and high humidity container of “Humidi Cabinet” LHL-112 manufactured by Tabay Espec. The temperature, humidity, and treatment time of the constant temperature and high humidity bath are 60 ° C. × 95% RH × 200 h, the impact strength is obtained by the same method as in item 4, the impact strength retention is obtained from the following formula, It was used as an index of degradability.
Impact strength retention rate (%) = (impact strength after treatment ÷ impact strength of untreated product) × 100

7). Thermal deformation temperature A bending test piece having a thickness of 1/8 inch (about 3.2 mm) was obtained under the conditions of a molding temperature of 250 ° C. and a mold temperature of 50 ° C. using an IS55EPN injection molding machine manufactured by Toshiba Machine. Next, according to ASTM method D648, the heat distortion temperature was determined under a load condition of 0.46 MPa.

8). Flowability The lowest molding that can obtain the shape of a square plate by molding a square plate of 80 mm x 80 mm x 1 mm thickness under the conditions of a molding temperature of 250 ° C and a mold temperature of 50 ° C using an IS55EPN injection molding machine manufactured by Toshiba Machine. The pressure was determined and the value was taken as the molding lower limit pressure. The fluidity is poorer as the molding lower limit pressure is higher.

[Reference example]
“/” In the resin names of the following Reference Examples means copolymerization, and “-g-” means graft.

(A) A-1: polylactic acid resin (poly L lactic acid resin having a D-form content of 1.2% and a weight average molecular weight in terms of PMMA of 160,000 was used).
(B) B-1: Branched aromatic polycarbonate resin (“IB-2500” manufactured by Idemitsu Petrochemical Co., Ltd.).
Aromatic polycarbonate resin having no branched structure: (“A-2500” manufactured by Idemitsu Petrochemical Co., Ltd.).
Carbon black: ("Printex" 35 manufactured by Tegusa Japan Co., Ltd.).

(C) Thermoplastic resin other than components (A) and (B) <C-1> Vinyl resin C-1-1: Poly (ethylene / ethyl acrylate / maleic anhydride) -g-polymethacryl Methyl acid (“Modiper” A-8200, manufactured by NOF Corporation).
C-1-2: Ethylene / glycidyl methacrylate-g-polymethyl methacrylate (“Modiper” A-4200 manufactured by NOF Corporation).
C-1-3: Silicone / acrylic composite core-shell rubber (“METABRENE” SX-005 manufactured by Mitsubishi Rayon Co., Ltd.).
C-1-4: Styrene / ethylene / butadiene / styrene (“Clayton” 1650 manufactured by Shell Chemical Co., Ltd.).
C-1-5: ABS resin (“Toyolac” T-100 manufactured by Toray Industries, Inc.).

<C-2> Thermoplastic polyester resin other than component (A) C-2-1: Polyester elastomer resin (“Hytrel” 4057 manufactured by Toray DuPont Co., Ltd.).
C-2-2: Polybutylene terephthalate ("Toraycon" 1401X31 manufactured by Toray Industries, Inc.).
C-2-3: Polyethylene (terephthalate / succinate) resin (DuPont "Biomax").
C-2-4: Polybutylene succinate resin (“Bionore” 1001 manufactured by Showa Polymer).

<C-3> Cellulose ester resin C-3-1: Cellulose acetate propionate ("CAP" manufactured by Eastman Chemical Co., acetate substitution degree 0.1, propionate substitution degree 2.93).

<C-4> Nylon resin C-4-1: Nylon 6 resin (“Amilan” CM1010 manufactured by Toray Industries, Inc.).
C-4-2: Nylon 6 / polyethylene glycol resin (“Pelestat” manufactured by Sanyo Chemical Industries, Ltd.).

<C-5> Polyolefin copolymer C-5-1: Ethylene / glycidyl methacrylate (“bond first” 2C manufactured by Sumitomo Chemical Co., Ltd.).

(D) Flame retardant <D-1>: condensed phosphate ester (“PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.).
<D-2>: Melamine cyanurate (“MC-440” manufactured by Nissan Chemical Industries, Ltd.).
<D-3>: Ammonium polyphosphate (“Fire Cut” FCP730 manufactured by Suzuhiro Chemical Co., Ltd.).
<D-4>: Melamine polyphosphate (“Melpua” 200 manufactured by DSM).
<D-5>: Zinc borate ("Firebreak" ZB manufactured by Borax).

(E) Fluororesin <E-1>: Tetrafluoroethylene (“Teflon” (registered trademark) 6-J manufactured by Mitsui DuPont Fluorochemical Co., Ltd.).
<E-2>: Acrylic-modified tetrafluoroethylene (Mitsubrene (registered trademark) “A-3800” manufactured by Mitsubishi Rayon Co., Ltd.).

(Other additives)
<Inorganic filler>: talc (“P-6” manufactured by Nippon Talc Co., Ltd., average particle diameter of about 4 μm).
<Epoxy compound 1>: Versatic acid glycidyl ester (Japan Epoxy Resin Co., Ltd. product "Cardura E10").
<Epoxy compound 2>: Bisphenol A diglycidyl ether (“Epicoat” 828 manufactured by Japan Epoxy Resin).
<Carbodiimide compound> (Nisshinbo Carbodilite HMV-8CA)
<Bisoxazoline compound>: Bisoxazoline / maleic anhydride-modified polyethylene (manufactured by Mikuni Pharmaceutical)
<Fiber reinforcement>: Glass fiber of chopped strand (CS-3J948 manufactured by Nitto Boseki Co., Ltd.).
<Plasticizer>: Polyethylene propylene glycol (“Pluronic” F68 manufactured by Asahi Denka Kogyo Co., Ltd.).
<Organized layered silicate>: ("MTE" manufactured by Coop Chemical Co., Ltd.).
<Antioxidant>: Hindered phenol-based antioxidant: pentaerythrityl-tetrakis {3- (3,5-t-butyl-4-hydroxyphenyl) propionate} ("Irganox" 1010 manufactured by Ciba Geigy Japan) ).
<Release agent 1>: Ethylene bisstearyl amide (EBA manufactured by NOF Corporation).
<Release agent 2>: Polypropylene / maleic anhydride wax (“Mitsui High Wax” NP0555A manufactured by Mitsui Chemicals, Inc.).

[Examples 1-41 and Comparative Examples 1-12]
(A) poly-L lactic acid resin, (B) branched aromatic polycarbonate resin, and (A) and (B) as required, with a D-form content of 1.2% and a PMMA equivalent weight average molecular weight of 160,000 (C) Thermoplastic resin, (D) Flame retardant, (E) Fluorine resin, carbon black and other additives other than the components are mixed in the proportions shown in Tables 1 to 5, respectively. Using a twin screw extruder, melt kneading is performed under conditions of a cylinder temperature of 250 ° C. and a screw rotation speed of 150 rpm. It was.

  In addition, the blending amounts of (C) thermoplastic resin, (D) flame retardant, (E) fluorine resin, carbon black and other additives other than the components (A) and (B) in Tables 1 to 5 are as follows: It is the compounding quantity with respect to 100 weight part of total amounts of (A) polylactic acid resin and (B) branched aromatic polycarbonate resin.

  Moreover, the characteristic shown to 1-8 of said [measurement method of each characteristic] was evaluated using the pellet of the obtained resin composition. These results are also shown in Tables 1 to 5.

  From Examples 1 to 6 in Table 1, the resin composition containing the components (A) and (B) of the present invention shows a sea-island structure, has excellent weld properties, and further contains 1 part by weight of carbon black. A thing is excellent in blackness.

  From Comparative Examples 1 to 6 in Table 1, a resin composition containing an aromatic polycarbonate resin having no branched structure instead of the component (B) shows a sea-sea structure, is inferior in weld physical properties, and further has carbon black 1 The resin composition blended by weight is inferior in blackness and can be said to have a color tone close to gray.

  From Examples 7 to 16 in Table 2 and Examples 17 to 19 in Table 3, the resin composition containing (C) a thermoplastic resin other than the components (A) and (B) shows a sea-island structure and is black. Excellent weld strength and weld elongation or any performance.

  Further, from Examples 20 to 23 in Table 3, the resin composition containing (C) the thermoplastic resin other than the ABS resin and / or the component (A) as the thermoplastic resin is further excellent in blackness and weld properties. It can be said that it is a resin composition.

  Moreover, the resin composition of Examples 7-23 has the impact strength of the same level or large impact strength with respect to Example 5 in which (C) thermoplastic resins other than the components (A) and (B) are not blended. An improved resin composition is obtained.

  In Examples 20 to 22, 1 part by weight of the release agent 2 polypropylene / maleic anhydride wax was blended in order to neutralize the alkali component in the ABS resin.

  From Comparative Examples 7 to 9 in Table 3, a resin composition comprising an aromatic polycarbonate resin having no branched structure instead of the component (B) and the component (C) exhibits a sea-sea structure, and has weld properties and blackness. Inferior to this, it can be said that the color tone is almost gray.

  From Examples 24-30 of Table 4, the resin composition which mix | blended the flame retardant (D) of this invention shows a sea-island structure, and the resin composition which is excellent in a flame retardance, maintaining the outstanding weld physical property and blackness. It's a thing.

  Further, (D) Example 27 and Example 33 in Table 4 in which flame retardant and inorganic filler talc were blended showed a sea-island structure without reducing impact strength, and maintained excellent weld properties and blackness. However, it can be said that the resin composition is excellent in flame retardancy.

  Moreover, the resin composition which mix | blended the talc of the inorganic filler of Examples 31-32 of Table 4 is excellent in blackness, showing a sea-island structure, and maintaining the outstanding weld physical property, without reducing an impact strength. It can be said that it is a resin composition.

  Moreover, the resin composition which mix | blended the flame retardant of Example 34 of Table 4 and Example 35 of Table 5 and an epoxy compound or a carbodiimide compound shows a sea island structure, and maintains the outstanding weld physical property and blackness. However, it was excellent in flame retardancy. Furthermore, when the hydrolyzability was compared with Example 26 in which no epoxy compound or carbodiimide compound was blended, the impact strength retention after wet heat treatment of Example 26 was 34%, Example 34 was 71%, and Example 35. Indicates a value of 86% and can be said to be a resin composition that improves hydrolyzability.

  Moreover, the resin composition which mix | blended the fiber reinforcement of Example 36 of Table 5 showed the sea island structure, and maintained the outstanding weld physical property and blackness. Furthermore, when the thermal deformation temperature was compared with Example 32 in which no fiber reinforcement was blended, Example 32 showed 94 ° C. and Example 36 showed 121 ° C., and the resin composition improved the thermal deformation temperature (heat resistance). It can be said that it is a thing.

  Moreover, the resin composition which mix | blended the plasticizer or organic layered silicate of Example 37 and Example 38 of Table 5 showed sea island structure, and maintained the excellent weld physical property and blackness. Furthermore, when the heat distortion temperature was compared with Example 32 in which no plasticizer or organic layered silicate was blended, Example 32 showed 94 ° C, Example 37 showed 108 ° C, Example 37 showed 114 ° C, It can be said that the resin composition improves the heat distortion temperature (heat resistance).

  Moreover, the resin composition which mix | blended the antioxidant of Example 39 of Table 5 showed sea island structure, and maintained the outstanding weld property and blackness. Furthermore, when the injection molded product of Example 32 and the injection molded product of Example 39, which did not contain an antioxidant, were put into a hot air dryer adjusted to 80 ° C. for 200 hours, Example 32 shows the surface of the molded product. Although cracks were observed in Example 39, Example 39 has no change on the surface of the molded product and can be said to be a resin composition that improves the heat aging resistance.

Moreover, the resin composition which mix | blended the mold release agent of Example 40 and Example 41 of Table 5 showed the sea island structure, and was maintaining the outstanding weld physical property and blackness. Furthermore, when the fluidity was compared with Example 32 in which no release agent was blended, the molding lower limit pressure of Example 32 was 45 kg / cm ² , Example 40 was 32 kg / cm ² , and Example 37 was 34 kg / cm. ² and can be said to be a resin composition that improves fluidity.

  From Comparative Examples 10 to 12 in Table 5, instead of the component (B), an aromatic polycarbonate resin having no branched structure, a resin composition containing the component (C) and the component (D), or the component (B) A resin composition containing an aromatic polycarbonate resin having no branched structure and talc as an inorganic filler exhibits a sea-sea structure, is inferior in weld physical properties and blackness, and can be said to have a color tone close to gray.

It is a schematic diagram which shows the aromatic polycarbonate resin which has the branched nucleus structure induced | guided | derived from the branching agent in this invention. [BRIEF DESCRIPTION OF THE DRAWINGS] It is a schematic diagram which shows an example of the sea island structure which (B) branched aromatic polycarbonate resin component disperse | distributes to an island shape in the sea component of (A) polylactic acid resin in this invention. (A) It is a schematic diagram which shows the dispersion structure of the aromatic polycarbonate resin which does not have a polylactic acid resin component and a branched structure.

Claims (8)

A resin composition comprising (A) 90 to 10% by weight of polylactic acid resin and (B) 10 to 90% by weight of branched aromatic polycarbonate resin, where the total amount of (A) and (B) is 100% by weight. A (A) component and a (B) component form a sea-island structure, and (B) a branched aromatic polycarbonate resin is dispersed in an island shape. 100% by weight of the total amount of (A) and (B), and (A) 90 to 10% by weight of a polylactic acid resin and (B) 10 to 90% by weight of a branched aromatic polycarbonate resin. A resin composition having a blackness of 25 or less when 1 part by weight of carbon black is blended with respect to parts by weight. Further, 1 to 70 parts by weight of (C) thermoplastic resin other than the components (A) and (B) is blended with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) branched aromatic polycarbonate resin. The resin composition according to any one of claims 1 to 2. The resin composition according to claim 3, wherein the thermoplastic resin (C) is a vinyl resin. Furthermore, (D) 1-50 weight part of flame retardants are mix | blended with respect to the total amount of 100 weight part of (A) polylactic acid resin (B) branched aromatic polycarbonate resin, Any one of Claims 1-4. The resin composition described in 1. 6. The resin composition according to claim 5, wherein the flame retardant (D) is at least one selected from a brominated flame retardant, a phosphorus flame retardant, a nitrogen compound flame retardant, a silicone flame retardant, and an inorganic flame retardant. . The molded article which consists of a resin composition of any one of Claims 1-6. The molded product according to claim 7, wherein the molded product is a housing of an OA device or an electrical device obtained by a multipoint gate.

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