CN105452377A - Polylactic acid-containing thermoplastic resin composition and molded product thereof - Google Patents
Polylactic acid-containing thermoplastic resin composition and molded product thereof Download PDFInfo
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- CN105452377A CN105452377A CN201480043004.6A CN201480043004A CN105452377A CN 105452377 A CN105452377 A CN 105452377A CN 201480043004 A CN201480043004 A CN 201480043004A CN 105452377 A CN105452377 A CN 105452377A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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Abstract
Provided is a polylactic acid-containing thermoplastic resin composition which enables the production of a molded article that can be molded in a practically satisfactory molding cycle and has excellent mechanical properties including impact resistance, excellent heat resistance, excellent weld appearance and the like. The polylactic acid-containing thermoplastic resin composition comprises: 100 parts by weight of a polylactic acid-containing thermoplastic resin component which comprises 50 to 95 parts by weight of a polylactic acid resin (A) and 5 to 50 parts by weight of a rubber-reinforced resin (B); 0.1 to 3 parts by weight of a nucleating agent (C); 1 to 15 parts by weight of a filler (D); and 0.03 to 3 parts by weight of a dispersant (E). The rubber-reinforced resin (B) comprises 30 to 100% by weight of a rubber-containing graft copolymer (b-1) and 0 to 70% by weight of a hard (co)polymer (b-2).
Description
[technical field]
The present invention relates to provide forming period short and the poly lactic acid series thermoplastic resin composition of the molding of the mechanical characteristicies such as shock-resistance, thermotolerance, excellent appearance and by this poly lactic acid series thermoplastic resin composition be shaped molding.
[background technology]
The rising of atmospheric carbon dioxide levels is pointed out as the major cause of Global warming, and advocates the necessity limiting Carbon emission in global scale.As carbon neutralization, effective utilization of the plant resources of absorption, stabilizing carbon dioxide receives publicity.
For plastics, also turn to the exploitation of the plastics utilizing biomass from the plastics of raw material based on oil in the past.These plastics receive publicity as biodegradable resin at first, start its meaning as department of botany's plastics of re-examine recently.
As practical expectation of the polylactic resin (PLA) of department of botany's plastics.Compared with existing petroleum plastics, the impact strength only comprising the plastics of polylactic resin is poor and forming period is long.
In order to improve the impact strength of polylactic resin system plastics, known can be blended by itself and rubber polymer.
The method using thermoplastic elastomer is described in patent documentation 1 (Japanese Unexamined Patent Publication 2002-37987 publication).The method of mixture modified conjugated diene polymer is described in patent documentation 2 (Japanese Unexamined Patent Publication 2005-226054 publication).The method of the segmented copolymer of mixture vinylbenzene and methacrylic ester is described in patent documentation 3 (Japanese Unexamined Patent Publication 2009-256403 publication).These methods have the effect improving impact strength.But die temperature is low, poly(lactic acid) improves under non-crystalline state, and compared with existing general-purpose plastics, thermotolerance is not all fully improved.
Following content is described: by adding crystallization nucleating agent in patent documentation 4 (Japanese Unexamined Patent Publication 2005-162867 publication) and patent documentation 5 (Japanese Unexamined Patent Publication 2005-272679 publication), make polylactic acid crystal, thus improve thermotolerance.But although facilitate crystallization by the interpolation of crystallization nucleating agent, crystallization time increases sometimes, and impact strength etc. do not improve yet.
To have illustrated in patent documentation 6 (Japanese Unexamined Patent Publication 2008-246954 publication) utilize raise die temperature, shaping that heating-method of cooling of sharply reducing temperature is after forming carried out.But the method is special manufacturing process, and curring time is elongated, it not general production method.
[prior art document]
[patent documentation]
Patent documentation 1: Japanese Unexamined Patent Publication 2002-37987 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2005-226054 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2009-256403 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2005-162867 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2005-272679 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2008-246954 publication
[summary of the invention]
[inventing problem to be solved]
The object of the present invention is to provide and can obtain can forming with forming period sufficient in practicality and the poly lactic acid series thermoplastic resin composition of the also excellent molding such as the mechanical characteristicies such as shock-resistance, thermotolerance, weld appearance, and by molding that this poly lactic acid series thermoplastic resin composition is shaped.
[for solving the means of problem]
The present inventor has actively carried out checking, the improvement of prior art hardy, found that following resin composition, this resin is utilized to form, polylactic resin crystallization and give thermotolerance at short notice can be made, and poly(lactic acid) also can keep shock-resistance etc. under the state of crystallization high state, and molding outward appearance is also excellent, thus completes the present invention.
Main points of the present invention are a kind of poly lactic acid series thermoplastic resin composition, it is for comprise poly lactic acid series thermoplastic resin elements 100 weight part of polylactic resin (A) 50 weight part ~ 95 weight part and rubber reinforced resin (B) 5 weight part ~ 50 weight part (wherein, what make polylactic resin (A) and rubber reinforced resin (B) adds up to 100 weight parts) in mixture nucleator (C) 0.1 weight part ~ 3 weight part, filler (D) 1 weight part ~ 15 weight part, and the poly lactic acid series thermoplastic resin composition of dispersion agent (E) 0.03 weight part ~ 3 weight part, it is characterized in that, this rubber reinforced resin (B) comprises graft copolymer (b-1) 30 % by weight ~ 100 % by weight containing rubber and hard (being total to) polymkeric substance (b-2) 0 % by weight ~ 70 % by weight.
Dispersion agent (E) is preferably used in combination of two or more.
Filler (D) more preferably shape is not the filler of needle-like, and preferable shape is the filler of needle-like is below 7 weight parts relative to poly lactic acid series thermoplastic resin elements 100 weight part.
Another main points of the present invention are the molding such poly lactic acid series thermoplastic resin composition of the present invention be shaped.
[effect of invention]
The appearance of molding poly lactic acid series thermoplastic resin composition shaping of the present invention obtained is excellent.The balance of the physical strengths such as the impact strength of this molding, rigidity, thermotolerance is good, and forming period is also short.Therefore, said composition is suitable for the purposes as various housing, structure unit.
Poly lactic acid series thermoplastic resin composition of the present invention expands the purposes of the polylactic resin as department of botany's resin, facilitates the practice with theory in carbon, can contribute to the reduction of carrying capacity of environment.
[embodiment]
Below describe embodiments of the present invention in detail.
In this specification sheets, " (being total to) is polymerized " refers to that " polymerization " is with both " copolymerization "." (methyl) vinylformic acid " refers to that " vinylformic acid " is with both " methacrylic acid ".
The weight-average molecular weight (Mw) of polylactic resin (A), the weight-average molecular weight (Mw) of hard (being total to) polymkeric substance (b-2), be will to be dissolved in tetrahydrofuran (THF) (THF) and to utilize gel permeation chromatography (GPC) to measure the molecular weight obtained containing the weight-average molecular weight (Mw) of the acetone soluble ingredient of the graft copolymer (b-1) of rubber and utilize polystyrene (PS) to convert the value represented.
[poly lactic acid series thermoplastic resin elements]
Poly lactic acid series thermoplastic resin elements comprises polylactic resin (A) and rubber reinforced resin (B).Rubber reinforced resin (B) only can comprise the graft copolymer (b-1) containing rubber, also can comprise the graft copolymer (b-1) containing rubber and hard (being total to) polymkeric substance (b-2).
{ polylactic resin (A) }
Polylactic resin (A) can utilize and the known means such as the method for lactic acid Direct Dehydration polycondensation or the method for rac-Lactide being carried out to ring-opening polymerization be obtained.
There are L body, D body, these 3 kinds of optical isomers of DL body in polylactic resin.In commercially available polylactic resin, have the purity of L body close to 100% polylactic resin, from the viewpoint of crystallization, the optical purity of the polylactic resin (A) used in the present invention preferably L body or D body is the polylactic resin of more than 98%.Polylactic resin (A) also can for the multipolymer containing other copolymer composition.
As other copolymer composition contained in polylactic resin (A), can enumerate: the diol compounds such as ethylene glycol, propylene glycol, butyleneglycol, heptanediol, hexylene glycol, ethohexadiol, nonanediol, decanediol, 1,4 cyclohexane dimethanol, neopentyl glycol, glycerine, tetramethylolmethane, dihydroxyphenyl propane, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol; Oxalic acid, succsinic acid, hexanodioic acid, sebacic acid, nonane diacid, dodecane two ketone acid, propanedioic acid, pentanedioic acid, cyclohexane dicarboxylic acid, terephthalic acid, m-phthalic acid, phthalic acid, naphthalene dicarboxylic acids, two (to carboxyl phenyl) methane, anthracene dicarboxylic acid, 4, the dicarboxylic acid such as 4 '-diphenyl ether dicarboxylic acid, 5-(sodium is for sulfo group) m-phthalic acid, 5-4-butyl-phosphonium m-phthalic acid; The hydroxycarboxylic acids such as oxyacetic acid, hydroxy-propionic acid, hydroxybutyric acid, hydroxypentanoic acid, hydroxycaproic acid, hydroxy-benzoic acid; The lactone etc. such as caprolactone, valerolactone, propiolactone, undecalactone, 1,5-oxepane-2-ketone.Usually be preferably less than 30 % by mole in the content of the copolymer composition whole monomer components in polylactic resin (A), be more preferably less than 10 % by mole.
About molecular weight, the molecular weight distribution of polylactic resin (A), be just not particularly limited as long as processing can be formed in fact.The weight-average molecular weight of polylactic resin (A) is generally more than 10,000, is preferably more than 50,000, more preferably more than 100,000.The upper limit of the weight-average molecular weight of polylactic resin (A) is not particularly limited, and is generally less than 400,000.
As mentioned above, the molecular weight of polylactic resin (A) can utilize GPC (solvent THF) to measure.At polylactic resin (A) in granular situation, sometimes be difficult to be dissolved in THF, in this case, can after being dissolved in chloroform, use methyl alcohol that component of polymer is separated out, this component of polymer is dry, dry thing is dissolved in THF, measures the molecular weight of soluble ingredient.Also can carry out as required heating etc. makes it dissolve.
From carbon neutralization aspect or improve shock-resistance, thermotolerance aspect consider, relative to total 100 weight part of polylactic resin (A) with rubber reinforced resin (B), the blend amount of the polylactic resin (A) in poly lactic acid series thermoplastic resin elements is 50 weight part ~ 95 weight parts, is preferably 60 weight part ~ 95 weight parts, is more preferably 70 weight part ~ 85 weight parts.If the blend amount of polylactic resin (A) is fewer than this scope, then cannot reach the object of the present invention effectively utilizing polylactic resin; If more than this scope, then cannot obtain the poly lactic acid series thermoplastic resin molding of excellent impact resistance.
Polylactic resin (A) can be used alone a kind, also can be used in combination by two or more.
As the concrete example of polylactic resin (A), " NATUREWORKS " that NatureWorks company manufactures can be enumerated, " REVODE " that the raw Biomatera Inc. of China sea manufactures etc.
{ rubber reinforced resin (B) }
Rubber reinforced resin (B) comprises the graft copolymer (b-1) containing rubber of graft polymerization hard on rubber polymer (being total to) polymkeric substance of 30 % by weight ~ 100 % by weight and hard (being total to) polymkeric substance (b-2) ((b-1) adds up to 100 % by weight with (b-2's)) of 0 % by weight ~ 70 % by weight.
< is containing graft copolymer (b-1) > of rubber
Graft copolymer (b-1) containing rubber is on rubber polymer in the ethene base system monomer such as graft polymerization vinyl cyanide base system monomer, aromatic vinyl base system monomer, (methyl) acrylic ester monomer at least a kind, usually have show with ABS, ASA, AES, MBS etc., on rubber polymer the structure of graft polymerization hard (being total to) polymkeric substance.
The rubber polymer formed containing the graft copolymer (b-1) of rubber is preferably butadiene-based rubber, the styrene/isoprene multipolymer equiconjugate diene series rubbers such as polyhutadiene, styrene/butadiene copolymers, acrylate/butadiene copolymers; The ethylene series such as acrylic rubber, the ethylene/propene copolymer rubber such as butyl polyacrylate; The silicon system rubber etc. such as organopolysiloxane, wherein, from the aspect of shock-resistance, particularly preferably polyhutadiene.These rubber polymers can be used alone a kind, or two or more is used in combination.
This rubber polymer can be polymerized by monomer.Rubber polymer can have core/shell structure, and such as can to have with polyhutadiene be core, take acrylate as the structure of shell.
The gel content of rubber polymer is preferably 50 % by weight ~ 99 % by weight, is more preferably 60 % by weight ~ 95 % by weight, is particularly preferably 70 % by weight ~ 85 % by weight.When gel content is within the scope of this, characteristic, the particularly impact strength of obtained poly lactic acid series thermoplastic resin composition can be improved.
In order to measure the gel content of rubber polymer, under room temperature (23 DEG C), the rubber polymer of weighing was dissolved in suitable solvent with 20 hours, then utilize 100 object wire nettings to carry out point getting, the insoluble composition remained on wire netting is weighed after dry 24 hours at 60 DEG C.Obtain insoluble composition relative to the ratio (% by weight) of dividing the rubber polymer before getting, as the gel content of rubber polymer.About solvent used in the dissolving of rubber polymer, when polyhutadiene preferred toluene, when butyl polyacrylate preferred acetone.
The particle diameter of rubber polymer is preferably 0.1 μm ~ 1 μm, is more preferably 0.2 μm ~ 0.5 μm, but is not limited thereto.The median size of rubber polymer can utilize optical means to measure before graft polymerization.After graft polymerization, can after utilizing staining agent to dye to rubber polymer, transmission electron microscope (TEM) be used to calculate median size.
Graft copolymer (b-1) containing rubber preferably can make 60 % by weight ~ 20 % by weight the monomer component of graft polymerization can carry out graft polymerization and obtain (what wherein, make rubber polymer and monomer mixture adds up to 100 % by weight) under the existence of the above-mentioned rubber polymer of 40 % by weight ~ 80 % by weight.When rubber polymer is more than above-mentioned lower value, the shock-resistance of the poly lactic acid series thermoplastic resin molding obtained is good.When rubber polymer is below above-mentioned higher limit, the reduction of shock-resistance, mobility etc. can be prevented.
It is one kind or two or more that the monomer component that can carry out graft polymerization on rubber polymer is preferably in vinyl cyanide base system monomer, aromatic vinyl base system monomer, methacrylate ester monomer, acrylic ester monomer, maleimide compound.
Vinyl cyanide base system monomer is preferably vinyl cyanide, methacrylic acid nitrile etc., particularly preferably vinyl cyanide.
Aromatic vinyl base system monomer is preferably vinylbenzene, alpha-methyl styrene, p-methylstyrene, bromstyrol etc., particularly preferably vinylbenzene, alpha-methyl styrene.
Methacrylate ester monomer is preferably methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate and their derivative etc., particularly preferably methyl methacrylate.
Acrylic ester monomer is preferably methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate and their derivative etc., particularly preferably methyl acrylate.
Maleimide compound is preferably N-phenylmaleimide, N-N-cyclohexylmaleimide etc.
These monomer components can comprise the monomer of modification that utilized functional group to carry out.As such monomer, such as, can enumerate the unsaturated carboxylic acids such as vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid.They can be used alone a kind, also can be used in combination by two or more.The usage ratio utilizing functional group to carry out the monomer of modification is preferably less than 30 % by weight relative to the total 100 % by weight of monomer component, is particularly preferably less than 10 % by weight.
About the monomer component be grafted on rubber polymer of the graft copolymer (b-1) containing rubber, in above-mentioned monomer, the combination of the particularly preferably combination of vinyl cyanide base system monomer and aromatic vinyl base system monomer, methacrylate ester monomer and acrylic ester monomer.
From the viewpoint of the shock-resistance improving the poly lactic acid series thermoplastic resin molding obtained further, in the combination of vinyl cyanide base system monomer and aromatic vinyl base system monomer, vinyl cyanide base system monomer is preferably vinyl cyanide, aromatic vinyl base system monomer is preferably vinylbenzene.The weight ratio of components of vinyl cyanide base system monomer and aromatic vinyl base system monomer be preferably 20/80 ~ 35/65 scope, be more preferably 25/75 ~ 30/70.By within the scope of this, dispersed, good thermal stability.
From the viewpoint of to improve further the poly lactic acid series thermoplastic resin molding obtained shock-resistance, improve weld appearance and then cooling time can be shortened simultaneously, in the combination of methacrylate ester monomer and acrylic ester monomer, methacrylate ester monomer is preferably methyl methacrylate, acrylic ester monomer is preferably methyl acrylate.The weight ratio of components of methacrylate ester monomer and acrylic ester monomer is preferably the scope of 100/0 ~ 50/50, more preferably 99/1 ~ 80/20.By within the scope of this, can shorten cooling time under the state keeping weld appearance, plasticity is good.
When rubber reinforced resin (B) only comprise graft copolymer (b-1) containing rubber and should containing the graft copolymer (b-1) of rubber in containing (methyl) acrylic resin composition, preferably in the monomer component grafting on rubber polymer of the graft copolymer (b-1) containing rubber containing (methyl) acrylic ester monomer.
Weight-average molecular weight containing the acetone soluble ingredient of the graft copolymer (b-1) of rubber is preferably 50000 ~ 600000, is more preferably 50000 ~ 550000, more preferably 100000 ~ 450000.By making the weight-average molecular weight of acetone soluble ingredient of the graft copolymer (b-1) containing rubber be more than above-mentioned lower value, the shock-resistance of the poly lactic acid series thermoplastic resin molding obtained becomes abundant.By making the weight-average molecular weight of acetone soluble ingredient of the graft copolymer (b-1) containing rubber be below above-mentioned higher limit, the shaping processability of poly lactic acid series thermoplastic resin composition becomes good.The polymer product of the monomer of that acetone soluble ingredient generates when being equivalent to graft polymerization monomer on rubber polymer, non-graft polymerization on rubber polymer.
Percentage of grafting ((acetone insoluble components weight/rubber polymer weight-1) × 100) containing the graft copolymer (b-1) of rubber is preferably 15 % by weight ~ 120 % by weight, is more preferably 20 % by weight ~ 85 % by weight.By making the percentage of grafting of the graft copolymer (b-1) containing rubber be more than above-mentioned lower value, the dispersiveness of rubber polymer, impact strength become good.By making the percentage of grafting of the graft copolymer (b-1) containing rubber be below above-mentioned higher limit, impact strength, plasticity become good.The multipolymer having carried out grafting can be not only the structure of the outside of rubber polymer, and can be contain the structure in inside.
Graft polymerization can be undertaken by letex polymerization, suspension polymerization, solution polymerization or mass polymerization, also can be the method combined by these polymerization processs.
As containing the graft copolymer (b-1) of rubber, also can by polymerization process, to become to be grouped into the different two or more graft copolymers containing rubber used in combination.
< hard (being total to) polymkeric substance (b-2) >
The monomer component used in hard (being total to) polymkeric substance (b-2) be preferably previous containing the graft copolymer (b-1) of rubber in one kind or two or more in the monomer introduced.Such as can use aromatic vinyl base system monomer, vinyl cyanide base system monomer and (methyl) acrylic ester monomer and use as required can with other monomer of these monomer copolymerizations.About formed hard (be total to) polymkeric substance (b-2) monomer component ratio, can other monomer etc. of copolymerization, can above-mentioned containing the graft copolymer (b-1) of rubber in use in the scope recorded.
The weight-average molecular weight (Mw) of hard (being total to) polymkeric substance (b-2) is preferably 30000 ~ 300000, more preferably 50000 ~ 250000.By making the weight-average molecular weight of rigid confocal thing (b-2) be more than above-mentioned lower value, the shock-resistance of the molding obtained becomes good; By for below above-mentioned higher limit, shaping processability becomes good.
Rubber reinforced resin (B) only can comprise the graft copolymer (b-1) containing rubber, also can comprise the graft copolymer (b-1) containing rubber and hard (being total to) polymkeric substance (b-2).By mixture hard (being total to) polymkeric substance (b-2), the characteristic such as thermotolerance, mobility can be improved.Relative to as rubber reinforced resin (B) containing the graft copolymer (b-1) of rubber and the total 100 % by weight of hard (being total to) polymkeric substance (b-2), when the blend amount of hard (being total to) polymkeric substance (b-2) is more than 70 % by weight, rubber content in rubber reinforced resin (B) reduces, and makes impact strength reduce thus.Therefore, as rubber reinforced resin (B) containing in the graft copolymer (b-1) of rubber and the total 100 % by weight of hard (being total to) polymkeric substance (b-2), the blend amount of hard (being total to) polymkeric substance (b-2) is 0 % by weight ~ 70 % by weight, preferably 0 % by weight ~ 50 % by weight, be more preferably 0 % by weight ~ 30 % by weight.
When mixture hard (being total to) polymkeric substance (b-2), the weight-average molecular weight of the acetone soluble ingredient that graft copolymer (b-1) and hard (being total to) polymkeric substance (b-2) containing rubber are combined is preferably 50000 ~ 600000, is particularly preferably 50000 ~ 550000, is especially preferably 100000 ~ 450000 as shown in the explanation of the previous graft copolymer (b-1) containing rubber.When the weight-average molecular weight of acetone soluble ingredient is more than above-mentioned lower value, the shock-resistance of the poly lactic acid series thermoplastic resin molding obtained becomes good; When this weight-average molecular weight is below above-mentioned higher limit, the shaping processability of poly lactic acid series thermoplastic resin composition becomes good.
Hard (being total to) polymkeric substance (b-2) can be used alone a kind, also can by used in combination for hard (being total to) polymkeric substance (b-2) of difference composition of more than two kinds, molecular weight.
< rubber content >
Rubber content in rubber reinforced resin (B), namely containing the graft copolymer (b-1) of rubber or be preferably 5 % by weight ~ 80 % by weight containing the content of the rubber polymer in the graft copolymer (b-1) of rubber and the mixture of hard (being total to) polymkeric substance (b-2), be particularly preferably 10 % by weight ~ 70 % by weight.By making the content of the rubber polymer in rubber reinforced resin (B) be more than above-mentioned lower value, sufficient shock-resistance can be obtained.Rubber reinforced resin (B) if in rubber polymer too much, then shock strength may reduce, and is thus preferably below above-mentioned higher limit.The content of the rubber polymer in rubber reinforced resin (B) can measure by using infrared spectroscopy determinator.
< (methyl) acrylic resin composition >
(methyl) acrylic resin composition can be contained as the graft copolymer (b-1) containing rubber of rubber reinforced resin (B) and/or the monomer component of the middle use of hard (being total to) polymkeric substance (b-2).By containing (methyl) acrylic resin composition in rubber reinforced resin (B), the effects such as shock-resistance raising, shortening cooling time improve further.
(methyl) acrylic resin composition can be enumerated as (methyl) vinyl cyanide, (methyl) acrylic ester monomer etc. in the above-mentioned monomer component illustrated in the monomer component being grafted on rubber polymer of the graft copolymer (b-1) containing rubber.(methyl) acrylic resin composition is preferably (methyl) acrylic ester monomer.
The content of (methyl) acrylic resin composition in rubber reinforced resin (B) is preferably 5 % by weight ~ 70 % by weight, is more preferably 10 % by weight ~ 50 % by weight, is particularly preferably 15 % by weight ~ 40 % by weight.When (methyl) acrylic resin component content in rubber reinforced resin (B) is more than above-mentioned lower value, can give full play of brought by mixture rubber reinforced resin (B) improvement shock-resistance, plasticity, cooling time shorten effect.When (methyl) acrylic resin component content in rubber reinforced resin (B) is below above-mentioned higher limit, the reduction of shock-resistance, plasticity can be prevented.
(methyl) acrylic resin composition is at least containing the monomer component of methacrylic ester as formation (methyl) acrylic resin composition.Be preferably the polymeric composition of the methacrylate ester monomers such as methyl methacrylate or the acrylic ester monomer such as methacrylate ester monomer and methyl acrylate and/or can the copolymer composition of other monomer of copolymerization.When containing (methyl) acrylic resin composition as (being total to) polymeric composition of methacrylic ester or methacrylic ester and acrylate, the part by weight of methacrylic ester and each monomer of acrylate is preferably 100/0 ~ 50/50, more preferably 99/1 ~ 80/20.When methacrylic ester is more than above-mentioned lower value, thermostability and the thermotolerance of the poly lactic acid series thermoplastic resin composition obtained become good.
The concrete example of the multipolymer of methyl methacrylate and methyl acrylate is " PARAPETG ", Mitsubishi Rayon Co., Ltd manufactured as Co., Ltd. KURARAY of commercially available product " ACRYPETVH ", " ACRYPETMD " that manufacture etc.By using they as hard (being total to) polymkeric substance (b-2) mixture in poly lactic acid series thermoplastic resin composition of the present invention, can make in rubber reinforced resin (B) containing (methyl) acrylic resin composition.
[nucleator (C)]
From the viewpoint of improving shock-resistance, thermotolerance, relative to total 100 weight part of polylactic resin (A) with rubber reinforced resin (B), the blend amount of the nucleator (C) in poly lactic acid series thermoplastic resin composition is 0.1 weight part ~ 3 weight part, is preferably 0.5 weight part ~ 2.5 weight part, is more preferably 0.5 weight part ~ 2 weight part.When the blend amount of nucleator (C) is less than this scope, polylactic resin crystallization rapidly cannot be made.When the blend amount of nucleator (C) is more than this scope, the poly lactic acid series thermoplastic resin molding of excellent impact resistance cannot be obtained.
Nucleator (C) is preferably the organic nucleating agent such as metal-salt, carboxylic acid amides of the sulfonated compounds such as metal salt of organic carboxylic acid, phenyl-phosphonic acid metal-salt, metallic rosinate, phosphate metal salt, phenylbenzimidazole sulfonic acid metal-salt such as Sodium Benzoate, but is not limited to these.
Nucleator (C) can be used alone a kind, also can be used in combination by two or more.
[filler (D)]
From the viewpoint of improving shock-resistance, thermotolerance and plasticity, relative to total 100 weight part of polylactic resin (A) with rubber reinforced resin (B), the blend amount of the filler (D) in poly lactic acid series thermoplastic resin composition is 1 weight part ~ 15 weight part, is preferably 3 weight part ~ 15 weight parts, is more preferably 5 weight part ~ 10 weight parts.Filler (D) if blend amount be less than this scope, then cooling time when being shaped may be elongated.Filler (D) if blend amount more than this scope, then cannot obtain the poly lactic acid series thermoplastic resin molding of shock-resistance and excellent appearance.Particularly preferred filler (D) is granular filler.
When filler (D) containing needle-like or tabular, relative to total 100 weight part of polylactic resin (A) with rubber reinforced resin (B), its content is preferably below 7 weight parts.If the blend amount of needle-like filler (D) is many, intensity when welding then likely is caused to reduce or degraded appearance, therefore, relative to total 100 weight part of polylactic resin (A) with rubber reinforced resin (B), the filler (D) of needle-like is preferably below 7 weight parts.
" needle-like " refers to the shape of so-called strip comprising " threadiness ", " bar-shaped ".
It is one kind or two or more that filler (D) is preferably in the mineral filler such as carbon fiber, glass fibre, talcum, wollastonite, calcium carbonate, silicon-dioxide.Also the organic fillers such as the fiber of the plant origin such as gombo hemp, bamboo fibers can be used.Can also by one kind or two or more used in combination with organic filler of one kind or two or more in mineral filler.
If filler (D) is oversize, then may impair plasticity, mobility, outward appearance; If undersized, then the effect of the improvement shock-resistance that possibly cannot obtain being brought by mixture filler (D), thermotolerance, forming period.It is following scope that the gravel size decision of filler (D) corresponds to its shape.
Granular filler: count 0.8 μm ~ 1.8 μm with median size.Median size is the value of the median particle diameter of D50.
The filler of needle-like: fiber length is 30 μm ~ 200 μm, fiber footpath is 3 μm ~ 10 μm.Fiber length is the value of the length utilizing the observable long leg of SEM to divide, and fiber footpath is the mean value of the major diameter in cross section.
The filler of tabular: median size is 3 μm ~ 10 μm, aspect ratio is 0.5 ~ 4.Median size is the value of the median particle diameter of D50.
[dispersion agent (E)]
From the viewpoint of improving shock-resistance, thermotolerance, plasticity, outward appearance, relative to total 100 weight part of polylactic resin (A) with rubber reinforced resin (B), the blend amount of the dispersion agent (E) in poly lactic acid series thermoplastic resin composition is 0.03 weight part ~ 3 weight part, is preferably 0.1 weight part ~ 3 weight part, is more preferably 0.1 weight part ~ 2 weight part.Dispersion agent (E) if blend amount be less than this scope, then cooling time when being shaped may be elongated.Dispersion agent (E) if blend amount more than this scope, then cannot obtain the poly lactic acid series thermoplastic resin molding of excellent heat resistance.
Spendable dispersion agent (E) is preferably glycerol fatty acid ester, polyglycerol fatty acid ester, sorbitan-fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycol fatty acid ester, polyethylene glycol dibenzoate, SUNSOFT 700P-2 diacetate esters, the ester classes such as montanate, ethylenebis fatty amide, ethylenebisstearamide, the amide compounds such as higher fatty acid polymeric amide, Zinic stearas, Magnesium Stearate, lithium stearate, calcium stearate, zinc phosphate, trimagnesium phosphate, Trilithium phosphate, the metal-salts such as calcium phosphate, the oil of hydrogenated castor wet goods plant origin, but be not limited to these.Dispersion agent (E) is particularly preferably glycerol fatty acid ester, calcium phosphate.
Dispersion agent (E) can be used alone a kind, also can be used in combination by two or more.From the aspect shortening cooling time, dispersion agent (E) preferably uses two or more.Dispersion agent (E) be more preferably more than a kind of metal-salt with more than a kind of dispersion agent in addition.For the reason shortening cooling time, weld appearance excellence, dispersion agent (E) share glycerol fatty acid ester and calcium phosphate.
When more than 1 of metal-salt kind is share with more than a kind of dispersion agent in addition, from the viewpoint of hydrolytic resistance, the ratio shared in the total of dispersion agent (E) of metal-salt is 5 % by weight ~ 50 % by weight, is in particular 7 % by weight ~ 35 % by weight.
[other composition]
In poly lactic acid series thermoplastic resin composition, except above-mentioned polylactic resin (A), rubber reinforced resin (B) (namely containing the graft copolymer (b-1) of rubber and hard (being total to) polymkeric substance (b-2) of mixture as required), nucleator (C), filler (D), dispersion agent (E), various additive, other resin can also be contained further.As various additive, that can enumerate in antioxidant, UV light absorber, lubricant, softening agent, stablizer, release agent, static inhibitor, tinting material (pigment, dyestuff etc.), fire retardant (halogen-system fire retardant, phosphorus flame retardant, antimony compounds etc.), anti-dripping agent, antiseptic-germicide, mould inhibitor, silicone oil, coupling agent, hydrolysis inhibitor etc. is one kind or two or more.
As other resin, HIPS resin can be enumerated, ASA resin, the rubber reinforcement phenylethylene resin series such as AES resin, AS resin, polystyrene resin, polycarbonate resin, nylon resin, methacrylic resin, polyvinyl chloride (PVC) RESINS, polybutylene terephthalate resin, pet resin, polyphenylene oxide resin, polyvinyl resin, PEN resin, acrylic resin, polytrimethylene terephthalate, polyphenylene sulfide, polyacetal resin, polyimide resin, phenol resins, melamine resin, silicone resin, unsaturated polyester resin, epoxy resin etc.Can be by the resin of these two or more resin alloys.Also can for the above-mentioned resin utilizing compatilizer or functional group etc. to carry out modification.
About the content of other resin above-mentioned in poly lactic acid series thermoplastic resin composition of the present invention, from the viewpoint of effectively utilizing polylactic resin (A), relative to poly lactic acid series thermoplastic resin elements 100 weight part, the content of this other resin is preferably below 50 weight parts, is particularly preferably below 30 weight parts.
[manufacture of poly lactic acid series thermoplastic resin composition and shaping]
In order to by poly lactic acid series thermoplastic resin composition granulating of the present invention, twin screw extruder, Banbury, warming mill etc. can be used, but be not limited to these.Wherein preferably utilize the melting mixing that twin screw extruder carries out.Also can by compounded resin or other additives such as side chargings.
Poly lactic acid series thermoplastic resin composition of the present invention can utilize the common manufacturing process such as injection forming, blow molding, sheet-like formed, vacuum forming to be configured as various molding.The moulding method of poly lactic acid series thermoplastic resin composition is particularly preferably injection molding method.
The automobile associated components such as backing plate, Outer Tyre, car bottom plate in household electrical appliances associated components, the luggage such as the molding of poly lactic acid series thermoplastic resin composition of the present invention can be suitable for the housing of the case member of the white domestic appliances such as refrigerator, washing machine or mobile telephone, seat fills, but be not limited to these.
Mix when preparing each composition of poly lactic acid series thermoplastic resin composition of the present invention or by these compositions, resin-lint etc. that is mixing, that produce when being shaped etc. directly can carry out fragmentation in this condition or according to circumstances afterwards for melting manipulation of regeneration.In this case, can reclaim in formation, also can carry out in addition reclaiming and used in combination as raw material in the manufacturing process of above-mentioned particle.
[embodiment]
Enumerate synthesis example, embodiment and comparative example below and further illustrate the present invention.Only otherwise exceed its main points, the present invention is by any restriction of following embodiment.
Hereinafter, " part " means " weight part ".
Weight-average molecular weight is measured by standard P S (polystyrene) scaling method of the GPC (gel permeation chromatograph, solvent: THF) using TOSOH Co., Ltd's manufacture.
The Microtrac9230UPA type that the median size of rubber polymer uses Nikkiso Company Limited to manufacture is obtained by dynamic light scattering method.
The FT-IR that the weight composition ratio of monomer uses Horiba Ltd to manufacture obtains.
[polylactic resin (A)]
Polylactic resin (a-1): polylactic resin (L body/D body=98/2 (weight ratio), weight-average molecular weight=140000, fusing point=171 DEG C)
[rubber reinforced resin (B)]
{ graft copolymer (b-1) containing rubber }
< synthesis example 1: containing the manufacture > of the graft copolymer (b-1-1) of rubber
According to following formula by the graft copolymer of emulsion polymerization synthesis containing rubber.
[formula]
Vinylbenzene (ST): 25 parts
Vinyl cyanide (AN): 10 parts
Polybutadiene latex: 65 parts (with solid component meter)
Nilox resin acid potassium: 1 part
Potassium hydroxide: 0.03 part
Tertiary lauryl mercaptan (t-DM): 0.04 part
Hydrogen phosphide cumene: 0.3 part
Ferrous sulfate: 0.007 part
Trisodium phosphate: 0.1 part
Crystalline dextrose: 0.3 part
Distilled water: 190 parts
In autoclave, drop into distilled water, nilox resin acid potassium, potassium hydroxide and polybutadiene latex (gel content 80 % by weight, median size 0.3 μm), after being heated to 60 DEG C, add ferrous sulfate, trisodium phosphate, crystalline dextrose.ST, AN, t-DM and hydrogen phosphide cumene was added continuously with 2 hours under the state being held in 60 DEG C.Be warming up to 70 DEG C afterwards, keep 1 hour, complete reaction.In the ABS latex be obtained by reacting by this, add antioxidant, utilize sulfuric acid to make it solidify afterwards, fully carry out drying after washing, obtain ABS graft copolymer (b-1-1).
< synthesis example 2: containing the manufacture > of the graft copolymer (b-1-2) of rubber
In the composition of raw materials of synthesis example 1, gel content is used to be that the polyhutadiene (median size 0.3 μm) 50 parts (using solid component meter) of 97 % by weight is as rubber polymer, vinylbenzene (ST) 37 parts as monomer is reacted with vinyl cyanide (AN) 13 parts, in addition, carry out graft polymerization in the same manner as synthesis example 1, obtain ABS graft copolymer (b-1-2).
< synthesis example 3: containing the manufacture > of the graft copolymer (b-1-3) of rubber
In the composition of raw materials of synthesis example 1, use butyl polyacrylate (gel content 65 % by weight, median size 0.34 μm) 60 parts (using solid component meter) as rubber polymer, make to react as the methyl methacrylate (MMA) 36 parts of monomer, methyl acrylate (MA) 4 parts, in addition, carry out graft polymerization in the same manner as synthesis example 1, obtain graft copolymer (b-1-3).
The measurement result of the weight-average molecular weight of the rubber content of the graft copolymer containing rubber manufactured in synthesis example 1,2,3, the weight composition ratio of monomer, percentage of grafting and acetone soluble ingredient is as described below.
Graft copolymer (b-1-1) containing rubber:
Rubber content=66.2 % by weight
AN/ST＝28/72
Percentage of grafting=40 % by weight
Weight-average molecular weight (Mw)=154000
Graft copolymer (b-1-2) containing rubber:
Rubber content=52.4 % by weight
AN/ST＝26/74
Percentage of grafting=57 % by weight
Weight-average molecular weight (Mw)=145000
Graft copolymer (b-1-3) containing rubber:
Rubber content=62.3 % by weight
MMA/MA＝90/10
Percentage of grafting=35 % by weight
Weight-average molecular weight (Mw)=70000
{ hard (being total to) polymkeric substance (b-2) }
< synthesis example 4: the manufacture > of rigid confocal thing (b-2-1)
Rigid confocal thing is synthesized as described below by suspension polymerization.
120 parts, water, sodium alkyl benzene sulfonate 0.002 part, polyvinyl alcohol 0.5 part, azoisobutyl cyanide 0.3 part, t-DM0.5 part and the monomer mixture containing vinyl cyanide (AN) 25 parts, vinylbenzene (ST) 25 parts, methyl methacrylate (MMA) 50 parts is dropped in reactor after nitrogen replacement.Heat successively adding portion is cinnamic simultaneously, be warming up to 120 DEG C with 5 hours from initial temperature 60 DEG C.After 4 hours 120 DEG C of reactions, take out polymkeric substance, obtain rigid confocal thing (b-2-1) further.
< synthesis example 5: the manufacture > of hard (being total to) polymkeric substance (b-2-2)
Use the monomer mixture containing vinyl cyanide (AN) 25 parts, vinylbenzene (ST) 75 parts, successively adding portion vinylbenzene, in addition, is polymerized in the same manner as synthesis example 4, obtains rigid confocal thing (b-2-2).
The weight composition ratio of monomer of the rigid confocal thing manufactured in synthesis example 4,5 and the measurement result of weight-average molecular weight (Mw) as described below.
Rigid confocal thing (b-2-1):
AN/ST/MMA＝23/28/49
Weight-average molecular weight (Mw)=113000
Rigid confocal thing (b-2-2):
AN/ST＝25/75
Weight-average molecular weight (Mw)=150000
[other additive]
Nucleator (C), filler (D), dispersion agent (E) use following substances.
{ nucleator (C) }
Nucleator (c-1): " EcopromotePPA-ZN " (phenylbenzimidazole sulfonic acid zinc (II)) that Misao Kusano manufactures
{ filler (D) }
Filler (d-1): " TP-A25 " (talcum (tabular), median size 5 μm, aspect ratio 2.0 of plate) that talcum Industrial Co., Ltd of Fuji manufactures
Filler (d-2): " NYGLOS8 " (long 136 μm of wollastonite (needle-like), fiber, 8 μm, fiber footpath) that Tomoe Engineering Co., Ltd. manufactures
Filler (d-3): " NS-1000 " (calcium carbonate (granular), median size 1.2 μm) that Dong efflorescence Industrial Co., Ltd manufactures
{ dispersion agent (E) }
Dispersion agent (e-1): " VR-02 " (glycerol fatty acid ester system tensio-active agent) that Taiyo Kagaku Co., Ltd. manufactures
Dispersion agent (e-2): " RIKAFLOWLA-100 " (polyethylene glycol dibenzoate) that New Japan Chem Co., Ltd manufactures
Dispersion agent (e-3): " HAP-08NP " (calcium phosphate) that MARUOCALCIUM Co., Ltd. manufactures
[manufacture of poly lactic acid series thermoplastic resin composition particle and evaluation]
Above-mentioned each composition is mixed by the mixed ratio shown in table 1,2; " CarbodiliteHMV-8CA " 0.3 part manufactured with the Nisshinbo Co., Ltd. as stablizer is further mixed together; twin screw extruder (" TEX-30 α " that JSW manufactures) is utilized to carry out melting mixing at 200 DEG C ~ 240 DEG C afterwards; and carry out granulating, make the particle of poly lactic acid series thermoplastic resin composition thus.
2 ounces of injection machines (Toshiba Corporation's manufacture) are utilized by obtained resin particle to form at 200 DEG C ~ 220 DEG C.Following method is utilized to measure shock-resistance (Charpy impact intensity), flexural strength, modulus in flexure, the thermotolerance (load deformation temperature) of the molding obtained.
Charpy impact intensity (KJ/m): ISO179 (normal temperature)
Flexural strength (MPa): ISO178 (normal temperature)
Modulus in flexure (MPa): ISO178 (normal temperature)
Load deformation temperature (DEG C): ISO75 (measuring load 0.45MPa)
Utilized by obtained resin particle 2 ounces of injection machines (Toshiba Corporation's manufacture) when forming for 200 DEG C ~ 220 DEG C, using the time till the tension specimen of ISO is removed as cooling time.
Tension specimen is configured as single cast gate sample and these two kinds of samples of double cast gate sample.For double cast gate sample, by visual confirmation weld appearance, evaluate by following benchmark.
◎: no-welding-seam, outward appearance are very good
Zero: almost no-welding-seam, outward appearance are good
×: there are weld seam, bad order
Carry out stretching according to ISO527 (normal temperature) to single cast gate sample and double cast gate sample to measure, calculate tensile strength × 100 of tensile strength/mono-cast gate sample of double cast gate sample as welding strength conservation rate.
[embodiment and comparative example]
The result of embodiment 1 ~ 10, comparative example 1 ~ 7 is shown in table 1,2.
[investigation]
Content is known as below by table 1,2.
The poly lactic acid series thermoplastic resin composition meeting the embodiment 1 ~ 10 of the prerequisite of the claims in the present invention can obtain the short and molding that the mechanical characteristicies such as shock-resistance, thermotolerance, welding strength etc. are also excellent of forming period.Particularly in the system that with the addition of two or more dispersion agent, forming period is short, and welding strength, weld appearance are excellent.
On the other hand, in the independent polylactic resin of comparative example 1, cooling time is long, and impact strength, thermotolerance are low.In comparative example 2, owing to not containing nucleator, dispersion agent, thus cooling time is long, other physical property is also poor, impracticable.Do not containing in the comparative example 3,4 of dispersion agent, although shorten cooling time, welding strength reduces, and weld appearance is also poor.Do not containing in Packed comparative example 5, cooling time is long, can not be referred to as fully in reality is shaped.With the addition of dispersion agent but adding number higher than in the comparative example 6 of scope of the present invention, welding strength, weld appearance are poor.In the comparative example 7 that the blend amount of polylactic resin is few, make that degree of crystallinity reduces, cooling time is long because poly(lactic acid) is few, weld appearance, welding strength conservation rate are also poor.
[industrial applicibility]
The forming period of molding poly lactic acid series thermoplastic resin composition of the present invention be shaped is short, and color developing, weld appearance are good, and the balance of the physical strengths such as shock-resistance, thermotolerance is also excellent.It is the material of the purposes be suitable for as various housing or structure unit using the molding that poly lactic acid series thermoplastic resin composition of the present invention is shaped.The molding that poly lactic acid series thermoplastic resin composition of the present invention is shaped be can be used in the multiple use of the applicable market requirement, its industrial applicibility is very high, and is also effective for reduction carrying capacity of environment.
Use specific mode to understand the present invention in detail, but it will be readily apparent to one skilled in the art that and can carry out various change when not departing from the intent and scope of the present invention.
The Japanese patent application 2013-219345 that the application submitted to based on October 22nd, 2013, quotes its full content by reference.
Claims (8)
1. a poly lactic acid series thermoplastic resin composition, it is for comprising the poly lactic acid series thermoplastic resin composition of poly lactic acid series thermoplastic resin elements 100 weight part, nucleator (C) 0.1 weight part ~ 3 weight part, filler (D) 1 weight part ~ 15 weight part and dispersion agent (E) 0.03 weight part ~ 3 weight part
This poly lactic acid series thermoplastic resin elements 100 weight part comprises polylactic resin (A) 50 weight part ~ 95 weight part and rubber reinforced resin (B) 5 weight part ~ 50 weight part, wherein polylactic resin (A) and rubber reinforced resin (B) add up to 100 weight parts;
This rubber reinforced resin (B) comprises graft copolymer (b-1) 30 % by weight ~ 100 % by weight containing rubber and hard (being total to) polymkeric substance (b-2) 0 % by weight ~ 70 % by weight, wherein containing rubber graft copolymer (b-1) and hard (being total to) polymkeric substance (b-2) add up to 100 % by weight.
2. poly lactic acid series thermoplastic resin composition as claimed in claim 1, wherein, mixture has described dispersion agent (E) of more than two kinds.
3. poly lactic acid series thermoplastic resin composition as claimed in claim 1, wherein, in described filler (D) 1 weight part ~ 15 weight part, needle-like filler is below 7 weight parts.
4. poly lactic acid series thermoplastic resin composition as claimed in claim 1, wherein, the described graft copolymer (b-1) containing rubber be 40 % by weight ~ 80 % by weight rubber polymer exist under make 60 % by weight ~ 20 % by weight the monomer component of graft polymerization can carry out graft polymerization, wherein, rubber polymer and monomer mixture add up to 100 % by weight.
5. poly lactic acid series thermoplastic resin composition as claimed in claim 4, wherein, described rubber polymer is polyhutadiene system rubber and/or acrylic rubber, and described monomer component is vinyl cyanide base system monomer and aromatic vinyl base system monomer or methacrylate ester monomer and acrylic ester monomer.
6. poly lactic acid series thermoplastic resin composition as claimed in claim 1, wherein, described rubber reinforced resin (B) containing 5 % by weight ~ 70 % by weight (methyl) acrylic resin composition as containing the graft copolymer (b-1) of rubber and/or the monomer component of hard (being total to) polymkeric substance (b-2).
7. poly lactic acid series thermoplastic resin composition as claimed in claim 2, wherein, described dispersion agent (E) is containing the dispersion agent beyond metal-salt and metal-salt, and the ratio of the metal-salt in this dispersion agent (E) is 5 % by weight ~ 50 % by weight.
8. a molding, it is shaped at the poly lactic acid series thermoplastic resin composition according to any one of claim 1 to 7.
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| JP2013219345A JP5737359B2 (en) | 2013-10-22 | 2013-10-22 | Polylactic acid-based thermoplastic resin composition and molded article thereof |
| JP2013-219345 | 2013-10-22 | ||
| PCT/JP2014/073735 WO2015060029A1 (en) | 2013-10-22 | 2014-09-09 | Polylactic acid-containing thermoplastic resin composition and molded product thereof |
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| CN105452377B CN105452377B (en) | 2016-12-07 |
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| ITUB20153298A1 (en) * | 2015-08-31 | 2017-03-03 | Bridgestone Corp | RUBBER COMPOUND FOR TREAD PRODUCTION |
| CN105567196B (en) * | 2015-12-15 | 2018-03-09 | 天津大学 | Toughness reinforcing has weak slow setting concurrently and controls the latex additive and preparation method of dehydration effect |
| JP5954507B1 (en) * | 2016-02-15 | 2016-07-20 | ユーエムジー・エービーエス株式会社 | Polylactic acid-based thermoplastic resin composition and molded article thereof |
| JP6692236B2 (en) * | 2016-07-14 | 2020-05-13 | 株式会社カネカ | Method for producing aliphatic polyester resin composition |
| JP6618188B2 (en) * | 2016-08-12 | 2019-12-11 | 株式会社Ｔｂｍ | Resin composition |
| WO2021132692A1 (en) * | 2019-12-26 | 2021-07-01 | Ｐｓジャパン株式会社 | Styrene resin composition, and molded body, sheet body and injection molded body each using same |
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| JP2008156616A (en) * | 2006-11-28 | 2008-07-10 | Toray Ind Inc | Resin composition and molded product made therefrom |
| JP2009079124A (en) * | 2007-09-26 | 2009-04-16 | Unitika Ltd | Biodegradable polyester resin composition and molded body formed of it |
| JP2009242520A (en) * | 2008-03-31 | 2009-10-22 | Riken Vitamin Co Ltd | Polylactic acid resin composition and molded article obtained by molding the same |
| JP5107873B2 (en) * | 2008-11-26 | 2012-12-26 | 花王株式会社 | Polylactic acid resin composition |
| JP2013032488A (en) * | 2011-06-27 | 2013-02-14 | Unitika Ltd | Thermoplastic resin composition |
| CN103635534A (en) * | 2011-06-29 | 2014-03-12 | 东丽株式会社 | Thermoplastic resin composition and molded article comprising same |
| JP5907698B2 (en) * | 2011-11-10 | 2016-04-26 | 三菱樹脂株式会社 | Aliphatic polyester resin sheet and plastic case for packaging container using the same |
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| JP2003286396A (en) * | 2002-01-24 | 2003-10-10 | Toray Ind Inc | Aliphatic polyester resin composition and molded article made therefrom |
| JP2007119730A (en) * | 2005-09-30 | 2007-05-17 | Toray Ind Inc | Resin composition and molded article composed of the same |
| CN101020780A (en) * | 2007-03-15 | 2007-08-22 | 上海交通大学 | Prepn process of polylactic acid-base thermoplastic wood-plastic composite material |
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| CN116348510A (en) * | 2020-10-23 | 2023-06-27 | 三菱化学株式会社 | Resin composition and molded article thereof |
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| WO2015060029A1 (en) | 2015-04-30 |
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