JP4957106B2 - Resin composition and molded article comprising the same - Google Patents

Description

  The present invention relates to a resin composition excellent in appearance without pearly luster, fluidity during molding and hydrolyzability, a resin composition exhibiting high flame retardancy, and a molded article comprising the same.

  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.

  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. ing.

  Patent Document 1 proposes blending polylactic acid as a method of modifying the fluidity of the aromatic polycarbonate resin. However, since the obtained material has a pearly luster, its application is limited, and there is a problem that the ballast effect is easily caused during melt-kneading and the productivity is poor.

  Patent Document 2 proposes that a polycarbonate be blended to improve the impact resistance of a polylactic acid resin.

  Patent Document 3 proposes a composition having excellent foamability in which a polyisocyanate compound is blended with a polylactic acid resin, polycarbonate, polystyrene, or the like.

  Patent Document 4 proposes a medical material in which a polyfunctional triazine compound is blended with a polymer such as polylactic acid resin or polycarbonate.

  However, the compositions of Patent Documents 2 to 4 have a problem that either the pearly luster or the fluidity at the time of molding, or the flame retardancy is difficult.

  Here, melt mixing two or more kinds of polymers is widely known as a polymer blend or a polymer alloy, and is widely used as a method for modifying the defects of individual polymers. However, in many cases where two or more kinds of polymers are melt-mixed, the strands are separated into individual phases due to differences in viscosity, molecular weight, molecular structure, etc., and have a coarse dispersion structure. In many cases, it is difficult to pelletize, and mixing unevenness due to phase separation is observed on the surface of the obtained injection-molded product.

  Since the polymer blend of the polylactic acid resin and polycarbonate of the present invention also has a phase separation structure that separates into individual phases, the above-described ballast effect during melt kneading and mixing unevenness due to phase separation are observed on the surface of the obtained injection molded product. It is presumed that the above-mentioned pearly luster, surface peeling and flow mark are caused.

  As a method for improving such phase separation, blending the following compatibilizers has been proposed.

Patent Document 5 proposes melting and mixing a radical reaction initiator in a polylactic acid resin and polycarbonate under a nitrogen atmosphere.
Moreover, since the polylactic acid resin and the aromatic polycarbonate resin are inferior in fluidity at the time of injection molding, it is difficult to obtain a thin molded product having a thickness of 1 mm or the like, and a method for improving both the compatibility and the fluidity. Was desired.

  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 5 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.
Japanese Patent No. 3279768 (page 1-2), (paragraph number [0008]) JP-A-11-140292 (page 1-2) JP 2000-17038 A (page 1-2) JP 2003-695 A (page 1-2) JP 2002-371172 A (page 1-2)

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

Accordingly, an object of the present invention is formed by blending at least one selected from polylactic acid resin and an aromatic polycarbonate resin and the oxazoline compound Contact and carbodiimide compound, is excellent in fluidity and hydrolytic resistance at no pearlescent molded A resin composition and a flame retardant are further blended to provide a resin composition exhibiting a high level of flame retardancy and a molded product comprising the same.

The present inventors have found that polylactic acid resin and an aromatic polycarbonate resin and the oxazoline compound Contact and carbodiimide compound of at least one by blending a resin composition selected, the resin composition was further blended a flame retardant, an object of the It has been found that it has excellent characteristics that meet the requirements of the present invention, and the present invention has been achieved.

That is, the present invention
(A) (A) 75 to 10% by weight of polylactic acid resin, (B) 25 to 90% by weight of aromatic polycarbonate resin, (C) Oxazoline compound with respect to 100 parts by weight of total amount of components (A) and (B) at least one of 0.1 to 15 parts by weight selected from monooleate and carbodiimide compound, and (a), (E) a condensed phosphate ester relative to 100 parts by weight of the total amount of component (B) from 0.5 to 100 A resin composition formed by blending parts by weight ,
(B) The resin composition according to (a), further comprising (D) a filler,
(C) The resin composition according to any one of (A ) to (B) , further comprising (F) a fluororesin.
(D) The resin composition according to any one of (A ) to (C) , further comprising (G) an epoxy compound,
(E) The resin composition according to any one of (a) to (d) , further comprising (H) a thermoplastic resin other than (A) polylactic acid resin and (B) polycarbonate resin,
(F) The resin composition according to any one of (a) to (e) , further comprising (I) a plasticizer.
( G) A molded article comprising the resin composition according to any one of (a) to (f) .

  The resin composition of the present invention has high flame retardancy by blending a resin composition excellent in fluidity and hydrolyzability during molding without pearl luster and a flame retardant. The molded article of the present invention comprising this resin composition can be effectively used for various applications such as mechanical mechanism parts, electrical / electronic parts, building members, automobile parts, and daily necessities, making use of the above-mentioned properties.

  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 contains 90% or more of polylactic acid containing 90% or more of L-form and D-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, The mechanical properties tend to be improved, 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 and molecular weight distribution of the polylactic acid resin is not particularly limited as long as it can be practically processed, 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 aromatic polycarbonate resin (B) in the present invention includes aromatic polycarbonate such as aromatic homo- or copolycarbonate obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester, and gel. Those having a weight average molecular weight in the range of 5000 to 500000 in terms of polymethyl methacrylate (PMMA) measured by permeation chromatography are preferably used, and the glass transition temperature measured by a differential calorimeter is in the range of 100 to 155 ° C. Those are preferably used.

  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.

  The blending amounts of the components (A) and (B) are (A) polylactic acid resin 75 to 10% by weight, (B) aromatic polycarbonate resin 25 to 90% by weight, and (A) polylactic acid resin 70 to 15% by weight. %, (B) 30 to 85% by weight of aromatic polycarbonate resin, (A) 65 to 20% by weight of polylactic acid resin, and (B) 35 to 80% by weight of aromatic polycarbonate resin are particularly preferable. .

  In the present invention, by blending (B) an aromatic polycarbonate resin, the heat distortion temperature of (A) polylactic acid resin can be increased, and the blending amount of (B) aromatic polycarbonate resin is less than 25% by weight. However, the above modification effect is insufficient, and if the blending amount of the aromatic polycarbonate resin (B) exceeds 90% by weight, the transparency becomes too strong, which is not preferable.

In the present invention and (C) an oxazoline compound Contact and carbodiimide compound is to modify the (A) polylactic acid resin, thereby compatibilizing (B) an aromatic polycarbonate resin and fluidity. Here, when the (A) component and the (B) component are melt-kneaded without blending the (C) component, there is a problem that the ballast effect is large and the melt strand is not drawn and the pelletization becomes difficult, or There is a problem that the appearance of the surface of the molded product is greatly impaired due to surface peeling, flow marks, and the like, and this is presumed to occur because the component (B) is not dispersed in the component (A) and is coarsely dispersed. The component (C) in the present invention improves the compatibility of the component (A) and the component (B), improves the problems during the melt kneading and the appearance of the molded product, and (B) the aromatic polycarbonate. It improves the fluidity of the resin.

Such, (C) oxazoline compound Contact and carbodiimide compounds may be used in one kind or two or more.

  The amount of component (C) is preferably 0.1 to 15 parts by weight, more preferably 0, per 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin. .2 parts by weight to 14 parts by weight, particularly preferably 0.3 parts by weight to 13 parts by weight. If the amount is less than 0.1 parts by weight, the effect of improving compatibilization and fluidity is small. This is not preferable because the characteristics deteriorate.

  The oxazoline compound is a compound having at least one oxazoline ring in the molecule. Specific examples of the oxazoline compound include 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propoxy-2. -Oxazoline, 2-butoxy-2-oxazoline, 2-pentyloxy-2-oxazoline, 2-hexyloxy-2-oxazoline, 2-heptyloxy-2-oxazoline, 2-octyloxy-2-oxazoline, 2-nonyloxy -2-oxazoline, 2-decyloxy-2-oxazoline, 2-cyclopentyloxy-2-oxazoline, 2-cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline, 2-methallyloxy-2-oxazoline, 2 -Crotyloxy- -Oxazoline, 2-phenoxy-2-oxazoline, 2-cresyl-2-oxazoline, 2-o-ethylphenoxy-2-oxazoline, 2-o-propylphenoxy-2-oxazoline, 2-o-phenylphenoxy-2- Oxazoline, 2-m-ethylphenoxy-2-oxazoline, 2-m-propylphenoxy-2-oxazoline, 2-p-phenylphenoxy-2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline 2-propyl-2-oxazoline, 2-butyl-2-oxazoline, 2-pentyl-2-oxazoline, 2-hexyl-2-oxazoline, 2-heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2 -Nonyl-2-oxazoline, 2-decyl-2-oxazoline, -Cyclopentyl-2-oxazoline, 2-cyclohexyl-2-oxazoline, 2-allyl-2-oxazoline, 2-methallyl-2-oxazoline, 2-crotyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-o -Ethylphenyl-2-oxazoline, 2-o-propylphenyl-2-oxazoline, 2-o-phenylphenyl-2-oxazoline, 2-m-ethylphenyl-2-oxazoline, 2-m-propylphenyl-2- Oxazoline, 2-p-phenylphenyl-2-oxazoline, 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (4 4'-dimethyl-2-oxazoline), 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis ( 4,4'-diethyl-2-oxazoline), 2,2'-bis (4-propyl-2-oxazoline), 2,2'-bis (4-butyl-2-oxazoline), 2,2'-bis (4-hexyl-2-oxazoline), 2,2'-bis (4-phenyl-2-oxazoline), 2,2'-bis (4-cyclohexyl-2-oxazoline), 2,2'-bis (4 -Benzyl-2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-o-phenylenebis (2- Oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-m -Phenylenebis (4-methyl 2-oxazoline), 2,2'-m-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-ethylenebis (2-oxazoline), 2,2'-tetramethylenebis (2 -Oxazoline), 2,2'-hexamethylene bis (2-oxazoline), 2,2'-octamethylene bis (2-oxazoline), 2,2'-decamethylene bis (2-oxazoline), 2,2 ' -Ethylenebis (4-methyl-2-oxazoline), 2,2'-tetramethylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-9,9'-diphenoxyethanebis (2 -Oxazoline), 2,2'-cyclohexylenebis (2-oxazoline), 2,2'-diphenylenebis (2-oxazoline) and the like. Among the oxazoline compounds, 2,2'-m-phenylene bis (2-oxazoline), 2,2'-p-phenylene bis (2-oxazoline) is used rather preferred.

  Furthermore, polymer compounds obtained by grafting or copolymerizing the above oxazoline compounds can also be preferably used. Specific examples include bisoxazoline / styrene / maleic anhydride copolymers, bisoxazoline / maleic anhydride modified polyethylene, bis Examples include oxazoline / 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 carbodiimide compound is a compound having at least one carbodiimide group represented by (—N═C═N—) in the molecule. As a production example, an organic isocyanate is heated in the presence of a suitable catalyst. And can be produced by a decarboxylation reaction. Further, it may be a compound in which isocyanate remains in the molecule.

  Specific examples of the carbodiimide compound include diphenylcarbodiimide, di-cyclohexylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, diisopropylcarbodiimide, dioctyldecylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, and di-p. -Nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di- 2,5-dichlorophenylcarbodiimide, p-phenylene-bis-o-toluylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenyle -Bis-di-p-chlorophenylcarbodiimide, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide, hexamethylene-bis-cyclohexylcarbodiimide, ethylene-bis-diphenylcarbodiimide, ethylene-bis-dicyclohexylcarbodiimide, N, N′-di-o-triylcarbodiimide, N, N′-diphenylcarbodiimide, N, N′-dioctyldecylcarbodiimide, N, N′-di-2,6-dimethylphenylcarbodiimide, N-triyl-N '-Cyclohexylcarbodiimide, N, N'-di-2,6-diisopropylphenylcarbodiimide, N, N'-di-2,6-di-tert-butylphenylcarbodiimide, N-toluyl-N'-phenylcarbodiimide, N , N'-Di-p-Nito Phenylcarbodiimide, N, N'-di-p-aminophenylcarbodiimide, N, N'-di-p-hydroxyphenylcarbodiimide, N, N'-di-cyclohexylcarbodiimide, N, N'-di-p-toluylcarbodiimide N, N'-benzylcarbodiimide, N-octadecyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-octadecyl-N'-tolylcarbodiimide, N-cyclohexyl-N'-tolylcarbodiimide, N -Phenyl-N'-tolylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, N, N'-di-o-ethylphenylcarbodiimide, N, N'-di-p-ethylphenylcarbodiimide, N, N'- Di-o-isopropylphenylcarbodiimide, N, '-Di-p-isopropylphenylcarbodiimide, N, N'-di-o-isobutylphenylcarbodiimide, N, N'-di-p-isobutylphenylcarbodiimide, N, N'-di-2,6-diethylphenylcarbodiimide N, N'-di-2-ethyl-6-isopropylphenylcarbodiimide, N, N'-di-2-isobutyl-6-isopropylphenylcarbodiimide, N, N'-di-2,4,6-trimethylphenyl Mono- or dicarbodiimide compounds such as carbodiimide, N, N′-di-2,4,6-triisopropylphenylcarbodiimide, N, N′-di-2,4,6-triisobutylphenylcarbodiimide, poly (1,6 -Hexamethylenecarbodiimide), poly (4,4'-methylenebiscyclohexylcarbodi) Imide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide), poly (4,4'-diphenylmethanecarbodiimide), poly (3,3'-dimethyl-4,4'- Diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (tolylcarbodiimide), poly (diisopropylcarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly ( And polycarbodiimides such as triethylphenylenecarbodiimide) and poly (triisopropylphenylenecarbodiimide). Of these, N, N′-di-2,6-diisopropylphenylcarbodiimide and 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide are preferable. Furthermore, there may be a mixture of the carbodiimide compound and the thermoplastic resin, a mixture of the carbodiimide compound and the end of the thermoplastic resin, or one or more of them.

  In the present invention, (D) a filler may be further blended. Examples of the filler (D) to be used include a plate-like, needle-like, granular or fibrous filler. Examples of the plate-like, needle-like or granular filler include (A) component, (B) component and (C) A filler that can be uniformly dispersed in the component is preferable, and a plate-like, needle-like, or granular filler obtained by pulverizing silicate mineral, silicate mineral, or various minerals by processing such as grinding is preferably used. It is done. Specific examples include bentonite, dolomite, barlite, finely divided silica, aluminum silicate, silicon oxide, dosonite, shirasu balloon, clay, sericite, feldspar powder, kaolin, zeolite (including synthetic zeolite), talc, mica and Examples include wollastonite (including synthetic wollastonite), glass flakes, glass beads, hydrotalcite, and silica.

  The plate-like, needle-like and granular fillers have the effect of increasing the tensile strength, and in particular, the average particle size is 10 μm or less, and there is little decrease in mechanical properties such as tensile elongation and bending deflection, More preferably, it is 5 μm or less. The lower limit is preferably an average particle size of 0.5 μm or more from the viewpoint of handling at the time of production, such as fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, aliphatic partially saponified ester, aminosilane, epoxysilane, etc. It may be treated with a coupling agent or the like.

  In addition, the needle-like filler such as wollastonite and kaolin preferably has an aspect ratio (average length / average diameter) of 3 to 20, and the average diameter is preferably 10 μm or less with less deterioration of mechanical properties, more preferably. The average diameter is preferably 5 μm or less. Among the plate-like, needle-like and granular fillers, talc and silica are preferably used because the obtained molded product has high whiteness. The average particle diameter is measured by a 50% cumulative distribution average particle diameter measured by a laser diffraction scattering method.

  Moreover, as a fibrous filler, what is normally used for reinforcement | strengthening of a thermoplastic resin can be used. 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, boron fiber and other inorganic fibrous fillers, polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, kenaf, Organic fibrous fillers such as ramie, cotton, jute, hemp, sisal, flax, linen, silk, Manila hemp, sugar cane, wood pulp, paper waste, waste paper and wool, among others, glass fiber and Acid aluminum whis Over the inorganic fibrous fillers, natural fibers such as kenaf from the viewpoint utilize the biodegradable polylactic acid resin is preferable. In addition, although fibrous fillers have a large decrease in mechanical properties such as tensile elongation and bending deflection, they have the effect of increasing the thermal deformation temperature, and are used for products that are used at high temperatures or products that need to be painted at high temperatures. Is preferred.

  The fibrous filler may be coated or focused with a thermoplastic resin such as an 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 or the like.

  Further, the blending amount of the filler (D) is preferably 1 to 200 parts by weight, and 2 to 100 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin. More preferably, if it is less than 1 part by weight, the effect of improving the strength and heat distortion temperature is small, and if it exceeds 200 parts by weight, mechanical properties such as tensile elongation and bending deflection are deteriorated.

In the present invention, it blends further (E) condensed phosphate ester.

Specific examples of the phosphate ester in the above condensed phosphate 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 Cid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, phenylphosphone include diethyl, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol a poly cresyl phosphate, a condensed phosphate, such as condensation products, such as hydroquinone poly (2,6-xylyl) phosphate be able to. Examples of commercially available condensed phosphate esters include PX-200, PX-201, PX-202, CR-733S, CR-741, and CR747 manufactured by Daihachi Chemical Co., Ltd. In particular, a condensed phosphate represented by the following formula (1) can be preferably used from the viewpoint of hydrolyzability.

(In the above formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ represent the same or different aromatic groups that do not contain halogen. X is selected from the following formulas (2) to (4): In the following formulas (2) to (4), R ^{1 to} R ⁸ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, Y represents a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, Ph represents a phenyl group, n in the formula (1) is an integer of 0 or more, and k and m in the formula (1) are Each of them is an integer of 0 or more and 2 or less, and (k + m) is an integer of 0 or more and 2 or less.) In addition, such aromatic condensed phosphates are different n or aromatic condensed phosphates having different structures. It may be a mixture of

  In the formula of the formula (1), n is an integer of 0 or more, and the upper limit is preferably 40 or less from the viewpoint of flame retardancy. Preferably it is 0-10, Most preferably, it is 0-5.

  K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less, preferably k or m is an integer of 0 or more and 1 or less, particularly preferably k or m. Is 1 respectively.

In the formulas (2) to (4), R ^{1 to} R ⁸ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and a neopentyl group. However, hydrogen, a methyl group, and an ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different aromatic groups containing no halogen. Examples of the aromatic group include aromatic groups having a benzene skeleton, a naphthalene skeleton, an indene skeleton, and an anthracene skeleton, and among them, those having a benzene skeleton or a naphthalene skeleton are preferable. These may be substituted with a halogen-free organic residue (preferably an organic residue having 1 to 8 carbon atoms), and the number of substituents is not particularly limited, but may be 1 to 3. preferable. Specific examples include phenyl groups, tolyl groups, xylyl groups, cumenyl groups, mesityl groups, naphthyl groups, indenyl groups, anthryl groups and the like, but phenyl groups, tolyl groups, xylyl groups, cumenyl groups, A naphthyl group is preferable, and a phenyl group, a tolyl group, and a xylyl group are particularly preferable.

  Of these, the following compounds (5) and (6) are preferable, and the compound (5) is particularly preferable.

(E) The compounding quantity of condensed phosphate ester is 0.5-100 weight part with respect to 100 weight part of total amounts of (A) polylactic acid resin and (B) aromatic polycarbonate resin, Furthermore, 1- 1 80 parts by weight is preferred.

  In the present invention, (F) a fluorine resin can be further blended. The (F) fluorine-based resin in the present invention is a resin containing fluorine in a substance molecule, specifically, polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, Tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, hexafluoropropylene / propylene copolymer, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymer, etc. Polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, polyvinylidene Fluoride is preferred, polytetrafluoroethylene and tetrafluoroethylene / ethylene copolymer are particularly preferred, polytetrafluoroethylene is more preferred, and polytetrafluoroethylene-containing mixed powder comprising polytetrafluoroethylene particles and an organic polymer The body 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, “Teflon (registered trademark)” 6C-J, and “Teflon (registered trademark)” 62 manufactured by Mitsui DuPont Fluorochemical Co., Ltd. -J, “Full-on” CD1 and CD076 manufactured by Asahi IC Fluoropolymers Co., Ltd. are commercially available. In addition, as a commercial product of a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer, it is commercially available as “Metabrene (registered trademark)” A series from Mitsubishi Rayon Co., Ltd. METABLEN (registered trademark) “A-3000”, “METABBRENE (registered trademark)” A-3800, and the like are commercially available. In addition, polytetrafluoroethylene “Teflon (registered trademark)” 6-J and the like are prone to agglomerate, so if they are mechanically strongly 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%.

  Moreover, the compounding quantity of (F) fluorine-type resin is 0.01-3 weight part with respect to 100 weight part of total amounts of (A) polylactic acid resin and (B) aromatic polycarbonate resin, Preferably it is 0. 0.02 to 2 parts by weight is preferable, more preferably 0.03 to 1 part by weight, and if the blending amount of the fluororesin exceeds 3 parts by weight, the fluidity and flame retardancy of the present invention are reduced, If it is less than 0.01, an effect for improving the flame retardancy is not recognized.

  In the present invention, (G) an epoxy compound can be further blended, and the (G) epoxy compound may be a monofunctional epoxy compound or a bifunctional or higher functional epoxy compound. It is preferable that it is the epoxy compound which has, for example, a glycidyl ester compound, a glycidyl ether compound, and a glycidyl ester ether compound is mentioned. One or more of these epoxy compounds can be used. 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 (G) epoxy compound 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, more preferably a composition capable of obtaining a monofunctional glycidyl ester compound. Excellent balance between viscosity stability and hydrolysis resistance.

  Moreover, the epoxy equivalent of (G) epoxy compound is preferably an epoxy compound of less than 500, more preferably an epoxy compound of less than 400 epoxy equivalent. Here, the epoxy equivalent is the number of grams of an epoxy compound containing 1 gram equivalent of an epoxy group. After dissolving the epoxy compound in pyridine, adding 0.05N hydrochloric acid and heating at 45 ° C., thymol blue and cresol are used as indicators. Using a mixed solution of red, it can be obtained by a method of back titrating with 0.05N caustic soda.

  In addition, (G) the epoxy compound has a great effect on improving the hydrolyzability without impairing the viscosity stability and mechanical properties, and the blending amount of the (G) epoxy compound is in terms of viscosity stability and hydrolyzability. From 0.01 to 10 parts by weight, preferably 0.05 to 9 parts by weight, more preferably 0.1 to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin. ~ 8 parts by weight. The (G) epoxy compound does not include a polymer compound obtained by grafting or copolymerizing a glycidyl compound.

  In the present invention, (J) an alkaline earth metal compound can be further blended, and (J) the alkaline earth metal compound is preferably an alkaline earth metal compound such as a magnesium compound, a calcium compound, or a barium compound. Can be mentioned. Examples of the alkaline earth metal compounds include hydroxides, oxides, carbonates, sulfates, acetates, acetates, lactates, oleic acid, palmitic acid, stearic acid, and montanic acid of alkaline earth metals. And organic acid salts. Specific examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium oxide, calcium oxide, barium oxide, magnesium carbonate, calcium carbonate, barium carbonate, magnesium sulfate, calcium sulfate. , Barium sulfate, magnesium acetate, calcium acetate, barium acetate, magnesium lactate, calcium lactate, barium lactate, and magnesium, calcium and barium salts of organic acids such as oleic acid, palmitic acid, stearic acid and montanic acid Is mentioned. Among these, hydroxides and carbonates of alkaline earth metals are preferably used. In particular, magnesium hydroxide and calcium carbonate are preferably used, and calcium carbonate is more preferably used. Such (J) alkaline earth metals can be used alone or in combination of two or more. In addition, calcium carbonate, light calcium carbonate, heavy calcium carbonate, wet-pulverized fine powder heavy calcium carbonate, wet heavy calcium carbonate (chalk), etc. are known depending on the production method. Included in the invention. These alkaline earth metal compounds may be treated with one or more surface treatment agents such as silane coupling agents, organic substances and inorganic substances, and the shape may be powder, plate or fiber. From the viewpoint of dispersibility, it is preferable to use it in a powder form having an average particle size of 10 μm or less. Further, if the particle size is fine, the effect of improving hydrolyzability is large and preferable.

In addition, as an effect of blending the (J) alkaline earth metal compound, a flame retardant, particularly a phosphorus-based flame retardant, is easily hydrolyzed, which adversely affects the hydrolyzability of the polylactic acid resin. In addition to the epoxy compound, By adding the alkaline earth metal compound in combination, the hydrolyzability is further improved by neutralizing the phosphoric acid generated from the hydrolyzed phosphorus-based flame retardant with the alkaline earth metal compound. It is estimated that In addition, when an alkali metal compound is used instead of the alkaline earth metal compound, the alkali metal compound is not preferred because it often has alkalinity and usually promotes hydrolysis of the polylactic acid resin. The alkaline earth metal compound used in the present invention is preferably insoluble in water in a neutral state and exhibits a neutralizing action by dissolving in an acidic environment when the phosphate ester is decomposed and the system becomes acidic. Used. The solubility in the neutral state is described in, for example, the Handbook of Chemistry, published by Maruzen Co., Ltd. (Showa 41), and the solubility in water is preferably 1 g / 100 g or less, more preferably 10 ⁻¹ g / 100 g water or less. Incidentally, the solubility of calcium carbonate most preferably used in water is 5.2 × 10 ⁻³ g / 100 g water.

  Further, the blending amount of (J) alkaline earth metal compound is 0 with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin from the viewpoint of mechanical properties and hydrolyzability. 0.01 to 10 parts by weight, preferably 0.05 to 9 parts by weight, more preferably 0.1 to 8 parts by weight.

  In the present invention, (A) a thermoplastic resin other than (A) polylactic acid resin and (B) aromatic polycarbonate resin can be further blended. Specific examples of (H) thermoplastic resin include polyester resin, phenoxy Resins, cellulose ester resins, polyamide resins, polyetherimide resins, styrene resins, and silicone compound-containing core-shell rubbers are more preferable, and polyester resins, cellulose ester resins, polyamide resins, styrene-based resins, and silicone compound-containing core-shell rubbers are particularly preferable.

  Moreover, the compounding quantity of said (H) thermoplastic resin is 0.5-200 weight part with respect to 100 weight part of total amounts of (A) polylactic acid resin and (B) polycarbonate resin, and also 1- The amount is preferably 150 parts by weight, and one or more parts are used.

  The polyester resin preferably used in the above (H) thermoplastic resin is (i) dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative, (b) hydroxycarboxylic acid or its ester-forming property. It is a polymer or copolymer obtained by polycondensation of one or more selected from derivatives, (c) lactones, and is a thermoplastic polyester resin other than polylactic acid resin.

  Examples of the dicarboxylic acid or ester-forming derivative thereof include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malon Examples thereof include aliphatic dicarboxylic acids such as acid, glutaric acid and dimer acid, alicyclic dicarboxylic acid units such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

  Examples of the diol or ester-forming derivatives thereof include aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, Aroma such as 6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol or the like, or a long chain glycol having a molecular weight of 200 to 100,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. Dioxy compounds such as 4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F, and the like And La ester forming derivatives.

Examples of the hydroxycarboxylic acid include glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and ester formation thereof. Sex derivatives and the like. Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Specific examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polypropylene terephthalate, polypropylene (terephthalate / isophthalate), polyethylene terephthalate, polyethylene (terephthalate / isophthalate), bisphenol A (Terephthalate / isophthalate), polybutylene naphthalate, polybutylene (terephthalate / naphthalate), polypropylene naphthalate, polypropylene (terephthalate / naphthalate), polyethylene naphthalate, polycyclohexanedimethylene terephthalate, polycyclohexanedimethylene (terephthalate / isophthalate) Phthalate), poly (cyclohexanedimethylene / ethylene) terephthalate , Aromatic polyesters such as poly (cyclohexanedimethylene / ethylene) (terephthalate / isophthalate), polybutylene (terephthalate / isophthalate) / bisphenol A, polyethylene (terephthalate / isophthalate) / bisphenol A, and polybutylene (terephthalate / succinate) ), Polypropylene (terephthalate / succinate), polyethylene (terephthalate / succinate), polybutylene (terephthalate / adipate), polypropylene (terephthalate / adipate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sulfoisophthalate / adipate), polyethylene ( Terephthalate / sulfoisophthalate / succinate), polypropylene ( Phthalate / sulfoisophthalate / succinate), polybutylene (terephthalate / sebate), polypropylene (terephthalate / sebate), polyethylene (terephthalate / sebate), polybutylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polyethylene terephthalate / polyethylene glycol, poly Butylene terephthalate / poly (tetramethylene oxide) glycol, polypropylene terephthalate / poly (tetramethylene oxide) glycol, polybutylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, polypropylene (terephthalate / isophthalate) / poly (tetramethylene) Oxide) glycol , Polybutylene terephthalate / poly (propylene oxide / ethylene oxide) glycol, Polypropylene terephthalate / poly (propylene oxide / ethylene oxide) glycol, Polybutylene (terephthalate / isophthalate) / Poly (propylene oxide / ethylene oxide) glycol, Polypropylene (terephthalate / isophthalate)・ Poly (propylene oxide / ethylene oxide) glycol, polybutylene (terephthalate / adipate), polypropylene (terephthalate / adipate), polybutylene terephthalate, poly-ε-caprolactone, etc. Polymer, polyethylene oxalate, polypropylene oxalate, poly Tylene oxalate, polyneopentyl glycol oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polybutylene adipate, polypropylene adipate, polyethylene adipate, polybutylene (succinate / adipate), polypropylene (succinate / adipate), polyethylene ( Succinate / adipate), polyhydroxyalkanoates such as polyhydroxybutyric acid and copolymers of β-hydroxybutyric acid and β-hydroxyvaleric acid, aliphatic polyesters such as polycaprolactone, polyglycolic acid, fats such as polybutylene succinate carbonate Group polyester carbonate, p-oxybenzoic acid / polyethylene terephthalate, p-oxybenzoic acid / 6-o Liquid crystalline polyesters such as copolyesters, such as shea-2-naphthoic acid.

  Among these, a polymer obtained by polycondensation of aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol or its ester-forming derivative as main components is preferable. Specifically, polybutylene terephthalate, polypropylene terephthalate , Polyethylene terephthalate, poly (cyclohexanedimethylene / ethylene) terephthalate, polypropylene naphthalate, polybutylene naphthalate, polybutylene (terephthalate / isophthalate), polypropylene (terephthalate / isophthalate), polyethylene (terephthalate / isophthalate), polybutylene terephthalate・ Polyethylene glycol, polypropylene terephthalate ・ Polyethylene glycol, polyethylene terephthalate ・ polyethylene glycol Polybutylene terephthalate / poly (tetramethylene oxide) glycol, polypropylene terephthalate / poly (tetramethylene oxide) glycol, polyethylene terephthalate / poly (tetramethylene oxide) glycol, polybutylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, Polypropylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, polybutylene (terephthalate / adipate), polypropylene (terephthalate / adipate), polyethylene (terephthalate / adipate), polybutylene (terephthalate / succinate), polypropylene (terephthalate / succinate) , Polyethylene (terephthalate / succinate It can be mentioned preferably. Ratio of aromatic dicarboxylic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer obtained by polycondensation of the above aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol or its ester-forming derivative as main components Is more preferably 30 mol% or more, and particularly preferably 40 mol% or more.

  Among these, a polymer obtained by polycondensation of terephthalic acid or an ester-forming derivative thereof and an aliphatic diol selected from ethylene glycol, propylene glycol, or butanediol or an ester-forming derivative thereof as a main component is more preferable. Specifically, polypropylene terephthalate, polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polypropylene (terephthalate / isophthalate), polyethylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene glycol, polyethylene terephthalate・ Poly (tetramethylene oxide) glycol, polypropylene terephthalate ・ Poly (teto Methylene oxide) glycol, polybutylene terephthalate / poly (tetramethylene oxide) glycol, polyethylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol, polypropylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, polybutylene (terephthalate) / Isophthalate) poly (tetramethylene oxide) glycol, polyethylene (terephthalate / succinate), polyethylene (terephthalate / adipate), polypropylene (terephthalate / succinate), polypropylene (terephthalate / adipate), polybutylene (terephthalate / succinate), polybutylene ( Terephthalate / adipate) That. The ratio of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer obtained by polycondensation of terephthalic acid or its ester-forming derivative and butanediol or its ester-forming derivative as a main component is 30 mol% or more. More preferably, it is particularly preferably 40 mol% or more.

  Preferred examples of the polyester 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, and particularly preferred examples include polybutylene terephthalate, polypropylene terephthalate, polybutylene terephthalate / poly (tetramethylene oxide) glycol, polyethylene ( Terephthalate / succinate), polybutylene sac At least one selected from the acid can be used, and may be used alone or in combination of two or more. By blending a polyester resin, flame retardancy, moldability, heat resistance A resin composition and a molded product with improved properties and mechanical properties can be obtained.

  Moreover, (H) The cellulose ester resin preferably used in a thermoplastic resin means that the hydroxyl group of cellulose is blocked with an esterifying agent. Specific esterifying agents include acid bases such as acetyl chloride and propionyl chloride, acid anhydrides such as acetic anhydride, pyropionic acid and butyric anhydride, carboxylic acid compound derivatives such as amide compounds and ester compounds, and ε- Examples of the cellulose ester resin include cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate phthalate. (A) Cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate from the viewpoint of compatibility or miscibility with polylactic acid resin Preferably, furthermore cellulose triacetate, and more preferably cellulose acetate propionate. 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 (H) polyamide resin preferably used in the thermoplastic resin is a thermoplastic polymer having an amide bond starting from an amino acid, lactam or diamine and a dicarboxylic acid.

  Examples of amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid. Examples of lactam include ε-caprolactam and ω-laurolactam.

  Examples of the diamine include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, 5-methylnonamethylene diamine, 2,4-dimethyloctamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3, 8-bis (aminomethyl) tricyclodecane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) ) Piperazine, Ami Such as ethyl piperazine, and the like.

  Dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5- Examples include sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid.

  Preferred polyamides used in the present invention include polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon). 6/10), polyhexamethylene dodecamide (nylon 6/12), polyundecane adipamide (nylon 11/6), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polytrimethylhexa Methylene terephthalamide, polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalamide / isophthalamide (nylon 6T / 6I), polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl) -4-aminocyclohexyl) methane dodecamide (nylon dimethyl PACM12), polymetaxylylene adipamide (nylon MXD6), polyundecamethylene terephthalamide (nylon 11T), polyundecamethylene hexahydroterephthalamide (nylon 11T (H )) And copolymers thereof with these polyalkylene glycols, mixed polyamides, polyamide elastomers, and the like. Among these, nylon 6, nylon 66, nylon 11, nylon 12, nylon 6/10, nylon 6/12, nylon 11/6 and copolymer polyamides such as copolymerization of these with polyethylene glycol, mixed polyamide, Polyamide elastomer is preferable, 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.

  In addition, from the problem of thermal stability of (A) polylactic acid resin and (B) polycarbonate resin, the polyamide resin used preferably has a melting point of 90 ° C. or higher and 240 ° C. or lower, and 100 ° C. or higher and 230 ° C. or lower. Is more preferable. Said polyamide resin may be used independently and may be used in mixture of 2 or more types.

  In the present invention, a resin composition and a molded product in which the moldability, mechanical characteristics, and heat resistance of the resin composition of the present invention are modified can be obtained by blending the polyamide resin.

  In addition, (H) a styrenic resin that is preferably used among thermoplastic resins is an aromatic vinyl compound such as α-methylstyrene, vinyltoluene, and divinylbenzene, and a vinyl cyanide compound such as acrylonitrile as components other than styrene. , (Meth) acrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, stearyl acrylate, maleimide, N-methyl maleimide, N-ethyl Maleimide monomers such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, diene compounds, maleic acid dialkyl esters, allyl alkyl ethers, unsaturated amino compounds, vinyl alkyl ethers, diene compounds Isoprene rubber or the like may be further copolymerized and is not limited, but specific examples of the styrene resin containing styrene include polystyrene resin, high impact polystyrene resin (high impact polystyrene resin), acrylonitrile / Styrene copolymers such as styrene copolymer (hereinafter abbreviated as AS resin), ABS resin, acrylate / styrene / acrylonitrile copolymer (AAS resin), acrylonitrile / ethylene / styrene (AES resin), SB resin, SBS resin, SEBS resin, etc. Examples include elastomers, and AS resin is particularly preferably used.

  The amount of styrene and acrylonitrile as main components in the preferably used AS resin is preferably at least 70% by weight or more, and the copolymerization ratio of styrene and acrylonitrile is 10% or more and less than 50% by weight. The amount of acrylonitrile is preferable, and the amount of acrylonitrile of 20% by weight or more and less than 40% by weight is more preferable. When the acrylonitrile content is in an appropriate range, particularly when a phosphorus-based flame retardant is used, a resin composition excellent in bleeding resistance and a molded product can be obtained.

  Examples of the silicone compound-containing core-shell rubber preferably used in (H) the thermoplastic resin include silicone-acrylic composite core-shell rubber.

  In the present invention, (I) a plasticizer can be further blended, and as the (I) plasticizer, known ones generally used as polymer plasticizers can be used without particular limitation. Agents, glycerin plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers and epoxy plasticizers.

  Specific examples of the polyester plasticizer include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, rosin, propylene glycol, 1,3-butanediol, 1,4 Examples thereof include polyesters composed of diol components such as butanediol, 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol, or may be end-capped with an epoxy compound or the like.

  Specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomonomontanate.

  Specific examples of polycarboxylic acid plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, and trimellitic acid. Tributyl ester such as tributyl, trioctyl trimellitic acid, trihexyl trimellitic acid, diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, adipic acid Adipic acid esters such as benzylbutyl diglycol, citrate esters such as triethyl acetylcitrate and tributyl acetylcitrate, azelaic acid esters such as di-2-ethylhexyl azelate, sebacin Dibutyl, and sebacic acid esters such as di-2-ethylhexyl sebacate and the like.

  Specific examples of the polyalkylene glycol plasticizer include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, bisphenols Polyalkylene glycols such as propylene oxide addition polymers, tetrahydrofuran addition polymers of bisphenols, or terminal-capped compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds.

  The epoxy plasticizer generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil, but there are also so-called epoxy resins mainly made of bisphenol A and epichlorohydrin. Can be used.

  Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, oleic acid Examples thereof include aliphatic carboxylic acid esters such as butyl, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, polyacrylic acid esters, and paraffins. As the plasticizer (I) used in the present invention, among those exemplified above, at least one selected from a polyester plasticizer and a polyalkylene glycol plasticizer is preferable, and two or more types may be used in combination. Good.

  The blending amount of (I) plasticizer is preferably in the range of 0.01 to 30 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin. The range of 1 to 20 parts by weight is more preferable, and the range of 0.5 to 10 parts by weight is particularly preferable.

  In the present invention, it is preferable to add (I) a plasticizer because moldability and heat resistance are improved without inhibiting flame retardancy.

  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, sorbitols, and ( A) A polymer nucleating agent having a melting point higher than that of the polylactic acid resin may be mentioned, and only one type may be used or two or more types may be used in combination.

  The compounding amount of the crystal nucleating agent is preferably 0.01 to 30 parts by weight, and 0.05 to 10 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 5 parts by weight is particularly preferable.

  In the present invention, (I) the plasticizer and the crystal nucleating agent may be used alone, but it is preferable to use both in combination in terms of moldability.

  In the present invention, (K) layered silicate can be further blended, and the formability can be improved. The (K) 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 the (K) layered silicate include various types such as smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and saconite, vermiculite, halloysite, kanemite, kenyaite, zirconium phosphate, titanium phosphate, and the like. Swelling mica such as clay minerals, Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, etc. are mentioned. Also good. 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.

  Examples of organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred. The ammonium ion may be any of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium, and examples of the primary ammonium ion include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, and benzyl ammonium. Examples of secondary ammonium ions include methyldodecylammonium and methyloctadecylammonium. Examples of tertiary ammonium ions include dimethyldodecylammonium and dimethyloctadecylammonium. Examples of quaternary ammonium ions include benzyltrimethylammonium, benzyltriethylammonium, Benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyl Benzyltrialkylammonium ions such as decadecammonium and benzalkonium, alkyltrimethylammonium ions such as trimethyloctylammonium, trimethyldodecylammonium, and trimethyloctadecylammonium, dimethyldialkyl such as dimethyldioctylammonium, dimethyldidodecylammonium, and dimethyldioctadecylammonium Examples thereof include ammonium ions, trialkylmethylammonium ions such as trioctylmethylammonium and tridodecylmethylammonium, and benzethonium ions having two benzene rings. In addition to these, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, amino at the terminal Examples also include ammonium ions derived from polyalkylene glycols having a group. Among these ammonium ions, preferred compounds include trioctylmethylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium and the like. These ammonium ions are generally available as a mixture, and the above compound names are representative compound names containing a small amount of analogs. These may be used alone or in combination of two or more.

  Further, those having a reactive functional group and those having high affinity are preferable, and ammonium ions derived from 12-aminododecanoic acid, polyalkylene glycol having an amino group at the terminal, and the like are also preferable.

  The layered silicate in which the exchangeable cation existing in the interlayer used in the present invention is exchanged with the organic onium ion is obtained by reacting the layered silicate having the exchangeable cation between the layer and the organic onium ion by a known method. Can be manufactured. Specifically, a method by an ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method by directly reacting a layered silicate with a liquid or melted ammonium salt may be used.

  In the present invention, the amount of organic onium ions relative to the layered silicate is determined by the cation exchange of the layered silicate in terms of the dispersibility of the layered silicate, the thermal stability during melting, the gas during molding, the suppression of odor generation, etc. Usually, the amount is in the range of 0.4 to 2.0 equivalents, preferably 0.8 to 1.2 equivalents with respect to the capacity.

  In addition to the above organic onium salts, these layered silicates are preferably pretreated with a coupling agent having a reactive functional group in order to obtain better mechanical strength. Examples of the coupling agent having a reactive functional group include isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds.

  In the present invention, the blending amount of (K) 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) polycarbonate resin. -30 parts by weight is more preferable, and 1-10 parts by weight is particularly preferable.

In the present invention, the resin is adjusted to various colors by adding one or more kinds of pigments and dyes of carbon black, titanium oxide, petal, ultramarine blue, calcined yellow, and various colors, and weather resistance (light) The blending amount of the pigment or dye is 0.01-20 with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin. Parts by weight, preferably 0.02 to 15 parts by weight, more preferably 0.03 to 10 parts by weight. In order to improve the dispersibility of the above-mentioned various color pigments and dyes, fatty acids, fatty acid metal salts, oxy fatty acids, fatty acid esters, partially aliphatic saponified esters, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acids Amides, aliphatic ketones, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters, fatty acid polyglycol esters, modified silicones and the like can be added as necessary, and (A) component, (B) component, and other It may be mastered by mixing with one or more thermoplastic resins.

  Examples of the carbon black include, but are not limited to, channel black, furnace black, acetylene black, anthracene black, oil smoke, pine smoke, and graphite. The average particle diameter is 10 μm or less, and dibutyl phthalate. Carbon black having an oil absorption of 50 to 400 cm 3/100 g is preferably used, and may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane coupling agent or the like as a treatment agent.

  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-described carbon black, titanium oxide, and various color pigments and dyes may be used in various thermoplastic resins in order to improve dispersibility with the flame retardant resin composition of the present invention and to improve handling during production. And may be used as a blended material that is melt blended or simply blended. In particular, the thermoplastic resin is preferably a polyester resin such as a polylactic acid resin, 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, Light stabilizers, UV absorbers, copper damage inhibitors, etc.), mold release agents (fatty acids, fatty acid metal salts, oxy fatty acids, fatty acid esters, aliphatic partially saponified esters, paraffin, 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.

The preparation method of the resin composition of the present invention, but are not particularly limited, selected from for example (A) polylactic acid resin, (B) a aromatic polycarbonate resin, (C) oxazoline compound Contact and carbodiimide compound After blending at least one kind and other additives such as (D) a filler and (E) a condensed phosphate ester in advance, (A) a single or twin screw extruder above the melting point of the polylactic acid resin. It is a method of uniformly melting and kneading.

Further, (A) the polylactic acid resin, (B) a aromatic polycarbonate resin, at least one, and (E) The resin composition of the present invention blended with a condensed phosphoric acid ester selected from (C) oxazoline compound Contact and carbodiimide compound Is capable of giving performances of V-2, V-1, V-0, 5V in a molded product having a flame retardance of 1.6 mm (1/16 inch) in accordance with UL standards. Can provide V-1, V-0, 5V performance, and in a more preferred embodiment, can provide V-0, 5V performance.

  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 product shapes and used, especially as mechanical parts, electrical / electronic parts, automobile parts, optical equipment, building / civil engineering materials, and daily products, especially mechanical mechanism parts. It is preferably used as a molded product of electric / electronic parts and automobile parts.

  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.

  Examples of mechanical mechanism parts include various types of bearings such as cleaning jigs, oilless bearings, stern bearings, and underwater bearings, motor parts, lighters, and typewriters.

  As electrical / electronic components, electrical equipment housings, OA equipment housings, various covers and housings, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, Variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, breaker, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD Chassis, motor brush holder, parabolic antenna, CD tray, cartridge, cassette, sorter, AC adapter, charging stand, switchboard, outlet cover, telephone related parts, facsimile related parts, copier related parts, PC Case and internal parts, CRT display case and internal parts, printer case and internal parts, mobile terminal cases and internal parts such as mobile phones and handheld mobiles, recording media (CD, DVD, PD, FDD, etc.) drive Housing and internal parts, copier housing and internal parts, facsimile housing and internal parts, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video cameras, audio・ Enclosures and interiors of audio equipment parts such as laser discs (registered trademark) and compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, electronic musical instruments, home game machines, portable game machines, etc. Examples include parts and parabolic antennas.

  Automotive parts can include interior parts, exterior parts, underhood parts, specifically instrument panels, trims, torque control levers, safety belt parts, register blades, washer levers, window regulator handles, window regulators. Handle knob, passing light lever, sun visor bracket, console box, trunk cover, spare tire cover, ceiling material, flooring, inner plate, seat material, door panel, door board, steering wheel, rearview mirror housing, air duct panel, Wind molding fastener, speed cable liner, sun visor bracket, headrest rod holder, various motor housings, various plates, various panels, roof rail, Ishia, fender, garnish, bumper, bumper corner, bumper skirt radiator grill, bonnet, door mirror stay, spoiler, hood louver, wheel cover, wheel cap, grill apron cover frame, lamp reflector, lamp bezel, door handle, door panel, side mirror Housing, center pillar, air outlet louver, emblem, exterior trim / mould, slide roof, tail lamp rim, precision machine related parts, alternator terminal, alternator connector, IC regulator, exhaust gas valve, various valves, fuel-related / exhaust system / Intake system pipes, air intake nozzle snorkel, engine coolant joint, carburetor main body, key Letter spacer, exhaust gas sensor, coolant 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, radiator grill, radiator Brush holder for motor, water pump impeller, 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, fuse connector, horn Terminals, electrical component insulation plates, step motor rotors, lamp sockets, solenoid bobbins, etc. Can be mentioned.

  Examples of the optical apparatus include a microscope, binoculars, a camera, and a clock.

  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.

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

[Examples 1 to 22 , Comparative Examples 1 to 64 ]
D-a content of 1.2%, weight average molecular weight of PMMA conversion is 160,000 (A) poly-L-lactic acid resin, shown in the following (B) an aromatic polycarbonate resin, (C) oxazoline compound Contact And at least one selected from carbodiimide compounds, fillers, flame retardants, fluororesins, epoxy compounds, alkaline earth metal salts, other thermoplastic resins, layered silicates, plasticizers, and other stabilizers, respectively. ~ Mixing at the ratio shown in Table 4, melt kneading with a 30mm diameter twin screw extruder under conditions of cylinder temperature 250 ° C and rotation speed 150rpm, drawing molten gut from the die into strands, and water cooling with cooling bath And the resin composition pelletized with the strand cutter was obtained.

Incidentally, Table 1 in Table 6 (B) an aromatic polycarbonate resin, (C) at least one selected from an oxazoline compound Contact and carbodiimide compound, (D) filler, (E) a flame retardant, (F) a fluorine-based resin , (G) epoxy compounds, (H) other thermoplastic resins, (I) plasticizers, (J) alkaline earth metal salts, (K) layered silicates, (L) other additives, The contents of In addition, the compounding quantity of (C)-(L) component is a compounding quantity with respect to 100 weight part of total amounts of (A) polylactic acid resin and (B) aromatic polycarbonate resin.
B-1: Aromatic polycarbonate resin (“A-1900” manufactured by Idemitsu Petrochemical Co., Ltd.)
C-1: Carbodiimide compound (Nisshinbo Carbodilite HMV-8CA)
C-2: Bisoxazoline / maleic anhydride modified polyethylene (manufactured by Mikuni Pharmaceutical)
C-3: (C) Carbodiimide compound (Nisshinbo “Carbodilite” LA-1).
C-4: (C) Carbodiimide compound ("Millionate" MTL manufactured by Nippon Polyurethane Industry Co., Ltd.).
Known modifiers: Other 1: Epoxidized soybean oil (“Kapox” S-6, manufactured by Kao Corporation).
Known modifiers: Other 2: Diisocyanate (diphenylmethane diisocyanate, “Millionate” MT manufactured by Nippon Polyurethane Industry Co., Ltd.).
D-1: talc (“P-6” manufactured by Nippon Talc Co., Ltd., average particle size of about 4 μm).
D-2: talc (“MS-P” manufactured by Nippon Talc Co., Ltd., average particle size of about 12 μm).
D-3: Glass fiber of chopped strand (CS-3J948 manufactured by Nitto Boseki Co., Ltd.).
E-1: condensed phosphate ester (“PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.).
E-2: Triphenyl phosphate (“TPP” manufactured by Daihachi Chemical Industry Co., Ltd.).
E-3: Melamine cyanurate (“MC-440” manufactured by Nissan Chemical Industries, Ltd.).
E-4: Ammonium polyphosphate (“Fire Cut” FCP730, manufactured by Suzuhiro Chemical Co., Ltd.).
E-5: Melamine polyphosphate (“Melpua” 200 manufactured by DSM).
E-6: Zinc borate ("Firebreak" ZB manufactured by Borax).
F-1: Tetrafluoroethylene (“Teflon (registered trademark)” 6-J manufactured by Mitsui DuPont Fluorochemical Co., Ltd.).
F-2: Acrylic modified tetrafluoroethylene ("Maybrene (registered trademark)" A-3800 manufactured by Mitsubishi Rayon Co., Ltd.).
G-1: Versatic acid glycidyl ester (“Cajura E10” manufactured by Japan Epoxy Resin Co., Ltd.)
G-2: Bisphenol A diglycidyl ether (“Epicoat” 828, manufactured by Japan Epoxy Resin).
H-1: Nylon 6 resin (“Amilan” CM1010 manufactured by Toray Industries, Inc.).
H-2: Polybutylene (terephthalate / adipate) resin ("Ecoflex" manufactured by BASF).
H-3: Silicone / acrylic composite core-shell rubber ("METABRENE" SX-005 manufactured by Mitsubishi Rayon Co., Ltd.).
H-4: Polyester elastomer resin (“Hytrel” 4057 manufactured by Toray DuPont Co., Ltd.).
H-5: AS resin (styrene / acrylonitrile = 74/26, manufactured by Toray Industries, Inc.).
H-6: Polybutylene terephthalate ("Toraycon" 1401X31 manufactured by Toray Industries, Inc.).
H-7: Polytrimethylene terephthalate resin ("Cortina" manufactured by Shell).
H-8: Polyethylene (terephthalate / succinate) resin ("Biomax" manufactured by DuPont).
H-9: Nylon 6 / polyethylene glycol resin (“Pelestat” manufactured by Sanyo Chemical Industries, Ltd.).
H-10: Polybutylene succinate resin (“Bionore” 1001 manufactured by Showa Polymer).
H-11: Polymethyl methacrylate resin (“SUMIPEX” LG35 manufactured by Sumitomo Chemical).
H-12: Polycaprolactone resin (“Placcel” H7 manufactured by Daicel Chemical Industries, Ltd.).
H-13: Cellulose acetate propionate ("CAP" manufactured by Eastman Chemical Co., acetate substitution degree 0.1, propionate substitution degree 2.93).
I-1: Ethylene bis lauric acid amide (“Slipax” L manufactured by NOF Corporation).
I-2: Polyethylene propylene glycol ("Pluronic" F68 manufactured by Asahi Denka Kogyo Co., Ltd.).
J-1 (alkaline earth metal salt): Calcium carbonate (“KSS1000” manufactured by Dowa Calfine Co., Ltd.).
K-1: Organized layered silicate (“MTE” manufactured by Corp Chemical Co., Ltd.).
L-1 (hindered phenol antioxidant): pentaerythrityl-tetrakis {3- (3,5-t-butyl-4-hydroxyphenyl) propionate} ("Irganox" 1010 manufactured by Ciba Geigy Japan, Inc.) .

  Further, the obtained resin composition was subjected to injection molding at a cylinder temperature of 240 ° C. and a mold temperature of 80 ° C. using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd. to obtain various molded products. ) To (5) were used to evaluate the characteristics.

(1) Molded product appearance (compatibility)
The surface appearance of a square plate having a thickness of 80 mm × 80 mm × 3 mm produced by injection molding was visually observed, and the presence or absence of pearly luster, surface peeling and flow mark and the degree thereof were evaluated according to the following guidelines. This evaluation can also be used as an index for judging the compatibility of the resin composition.
A: There is no pearly luster, no surface peeling and no flow mark, and the indoor fluorescent lamp line looks clear.
○: Although there is no pearly luster, surface peeling or flow mark, the indoor fluorescent lamp line looks unclear.
(Triangle | delta): Although pearl luster and surface peeling do not generate | occur | produce, a flow mark is recognized.
X: Nacreous or surface peeling is recognized.

(2) Fluidity A square plate having a thickness of 80 mm × 80 mm × 1 mm was formed by injection molding, and the lowest molding pressure at which the shape of the square plate could be obtained was determined. The fluidity is poorer as the molding lower limit pressure is higher. In the samples of the examples, the molding conditions other than the molding pressure were the same.

(3) Flame retardance Using test pieces of 127 mm x 12.7 mm x 0.8 mm (5 inches x 1/2 inches x 1/32 inches) produced by injection molding, an American UL standard subject 94 (UL94) Combustion test is performed in accordance with the vertical combustion test method, flame retardancy is evaluated, and the evaluation rank is indicated by V-0, V-1, V-2 in the order of excellent flame retardancy, and corresponds to the above rank The thing which did not do was made out of specification.

(4) Hydrolyzability A 3 mm thick ASTM No. 1 dumbbell test piece produced by injection molding was placed in a constant temperature and high humidity container of “Humidy Cabinet” LHL-112 manufactured by Tabay Espec. The conditions of the temperature and humidity of the constant temperature and high humidity and the treatment time are 60 ° C. × 95% RH × 200 h, a tensile test is performed according to ASTM method D638, the tensile strength retention is obtained from the following formula, and hydrolyzability is obtained. It was used as an index.
Tensile strength retention rate (%) = (Tensile strength after treatment ÷ Tensile strength of untreated product) × 100

(5) Thermal deformation temperature A thermal deformation test was performed under a load condition of 1.82 MPa according to ASTM method D648 using a 3 mm-thick test piece produced by injection molding.

  These results are also shown in Tables 1 to 6.

The resin composition in which the blending amount of the carbodiimide compound of component (C) shown in Comparative Example 12 of Table 1 exceeds the range of the present invention, the strand discharged from the die at the time of kneading is not stable, making it difficult to take out and obtaining a product. could not.

The resin composition in which the blending amount of the bisoxazoline / maleic anhydride-modified polyethylene (C) component shown in Comparative Example 13 in Table 1 exceeds the range of the present invention is such that the surface of the molded product becomes avatar-like, and the pearl luster and surface peeling The visual judgment of the appearance of the molded product was evaluated as x because it was difficult to judge and the value as a product was greatly impaired.

Moreover, the surface of a molded article also becomes an avatar-like shape for a composition in which epoxidized soybean oil as a known modifier of Comparative Examples 14 to 15 in Table 1 and diphenylmethane diisocyanate as a diisocyanate compound are blended, and determination of pearl luster and surface peeling However, the visual judgment of the appearance of the molded product was x because it was difficult and the value as a product was greatly impaired. Furthermore, the improvement effect of hydrolyzability was not recognized.

Comparative Examples 16 to 28 in Table 2 are resin compositions in which (H) another thermoplastic resin was blended in place of the (C) component, but the appearance of the molded articles was insufficient.

Examples 1 to 11 in Table 4 and Examples 12 to 22 in Table 6 are resin compositions further blended with (E) a flame retardant, are excellent in appearance and fluidity of molded products, and are imparted with flame retardancy. It can be said that it is a molded product.

In particular, from Examples 1 and 12 , the material using a specific condensed phosphate ester exhibited excellent flame retardancy with a small amount.

Further, from Examples 2 to 7 and Examples 13 to 18 , the material further blended with (F) fluorine-based resin shows no drip at the time of combustion, exhibits a higher flame retardancy V-0, and is flame retardant. It can be said that there is an effect of improving the property.

Further, from Examples 4 to 7 and Examples 15 to 18 , the material further blended with the (G) epoxy compound is further excellent in hydrolyzability while maintaining the performance and flame retardancy of the present invention, and is an alkaline earth metal. The material combined with a salt or a hindered phenolic antioxidant showed a higher degree of hydrolyzability.

Examples 8 to 11 and Examples 19 to 22 are resin compositions in which (D) glass fiber as a fibrous filler, (I) a plasticizer, and (K) a kind of organically modified layered silicate are blended. Thus, it can be said that there is an effect of modifying the heat distortion temperature while maintaining the performance and flame retardancy of the present invention. In particular, (D) glass fiber as a fibrous filler had a high effect of modifying the heat distortion temperature.

Claims (7)

(A) polylactic acid resin 75 to 10 wt%, (B) an aromatic polycarbonate resin 25-90 wt%, (A), (B ) the total amount per 100 parts by weight of (C) an oxazoline compound of the component you and 0.1 to 15 parts by weight of at least one selected from carbodiimide compounds , and 0.5 to 100 parts by weight of (E) condensed phosphate ester with respect to 100 parts by weight of the total amount of components (A) and (B) A resin composition. Furthermore, the resin composition of Claim 1 formed by mix | blending (D) filler. Furthermore, the resin composition of any one of Claims 1-2 formed by mix | blending (F) fluorine-type resin. Furthermore, (G) The resin composition of any one of Claims 1-3 formed by mix | blending an epoxy compound. Furthermore, the resin composition of any one of Claims 1-4 formed by mix | blending 1 or more types of (H) thermoplastic resins other than (A) polylactic acid resin and (B) polycarbonate resin. Furthermore, the resin composition of any one of Claims 1-5 formed by mix | blending (I) a plasticizer. A molded article comprising the resin composition according to any one of claims 1 to 6 .