WO2009107504A1 - ポリ乳酸樹脂組成物 - Google Patents
ポリ乳酸樹脂組成物 Download PDFInfo
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- WO2009107504A1 WO2009107504A1 PCT/JP2009/052563 JP2009052563W WO2009107504A1 WO 2009107504 A1 WO2009107504 A1 WO 2009107504A1 JP 2009052563 W JP2009052563 W JP 2009052563W WO 2009107504 A1 WO2009107504 A1 WO 2009107504A1
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- Prior art keywords
- polylactic acid
- group
- acid resin
- resin composition
- parts
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- 0 CC(C)(CC(CC1(C)C)OC(OC(CC2(C)C)CC(C)(C)N2O*C=C)=O)N1OC Chemical compound CC(C)(CC(CC1(C)C)OC(OC(CC2(C)C)CC(C)(C)N2O*C=C)=O)N1OC 0.000 description 1
Classifications
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
Definitions
- the present invention relates to a polylactic acid resin composition (hereinafter also simply referred to as “resin composition”), and more particularly to a polylactic acid resin composition containing a hindered amine compound having a specific structure.
- polylactic acid resin Since polylactic acid resin has a high melting point and can be melt-molded, it is being studied for various uses as a practically excellent biodegradable polymer. However, the polylactic acid resin has a problem in terms of weather resistance. For example, when the polylactic acid resin is left in sunlight, there is a problem that the polylactic acid resin deteriorates remarkably.
- Patent Document 1 discloses that a polylactic acid resin is blended with an ultraviolet absorber or a hindered amine compound.
- Patent Document 2 discloses a compound having an alkyloxyamine structure.
- Patent Document 3 discloses hindered amine compounds having a carboxylic acid ester structure, an amide structure, a carbamate structure, and an acetal structure as low basic hindered amine compounds having various skeletons. JP-A-6-184417 Japanese Patent Publication No.49-40557 Japanese Unexamined Patent Publication No. 1-1113368
- Patent Documents 2 and 3 there is no specific description that the hindered amine compound is applied to the polylactic acid resin, and there is no indication of the effect of suppressing the crystallization of the polylactic acid resin. Furthermore, even if a hindered amine compound proposed as a prior art as described in these patent documents is used for a polylactic acid resin, the effect of improving weather resistance has not been sufficiently obtained.
- an object of the present invention is to provide a polylactic acid resin composition that has solved the above-described problems and has excellent weather resistance and suppressed crystallization, and a resin molded product using the polylactic acid resin composition. There is to do.
- the present inventors have blended a hindered amine compound having a specific structure with a polylactic acid resin to improve weather resistance and suppress crystallization.
- the inventors have found that a resin composition and a resin molded product thereof can be obtained, and have completed the present invention.
- the polylactic acid resin composition of the present invention has the following general formula (1) with respect to 100 parts by mass of the polylactic acid resin.
- R 1 , R 2 , R 3 and R 4 each independently represents an alkyl group having 1 to 4 carbon atoms, and R represents an alkyl group having 1 to 18 carbon atoms which may be substituted with a hydroxyl group
- a hindered amine compound having a partial structure represented by an acyl group having 1 to 18 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms It is what.
- the hindered amine compound having a partial structure represented by the general formula (1) is represented by the following general formula (2), (In the formula, R is preferably the same as the general formula (1)).
- the resin molded product of the present invention is characterized in that the polylactic acid resin composition of the present invention is molded.
- the above configuration makes it possible to realize a polylactic acid resin composition having excellent weather resistance and suppressed crystallization. Therefore, a resin molded product using this polylactic acid resin composition is excellent in weather resistance and does not have the problem of cloudiness accompanying crystallization.
- polylactic acid resin composition of the present invention will be described in detail.
- examples of the polylactic acid resin used in the present invention include polylactic acid homopolymers, polylactic acid copolymers, and blend polymers of polylactic acid homopolymers and polylactic acid copolymers. Further, a blend polymer mainly composed of polylactic acid may be used as long as the effects of the present invention are not impaired.
- the weight average molecular weight (Mw) of such a polylactic acid resin is usually 50,000 to 500,000, preferably 100,000 to 250,000 in terms of polystyrene by gel permeation chromatography analysis.
- Mw weight average molecular weight
- the constituent molar ratio (L / D) of the L-lactic acid unit and the D-lactic acid unit in the polylactic acid resin is not particularly limited and can be selected from the range of 100/0 to 0/100. .
- L-lactic acid unit or D-lactic acid unit should be 75 mol% or more, and in order to obtain a polylactic acid resin composition having a higher melting point, L- It is preferable that either the lactic acid unit or the D-lactic acid unit is 90 mol% or more.
- the polylactic acid resin in the present invention is preferably a copolymer obtained by copolymerizing a lactic acid monomer or lactide and another copolymerizable component.
- examples of other components include dicarboxylic acids having at least two ester bond-forming functional groups, polyhydric alcohols, hydroxycarboxylic acids, lactone acids, and various polyesters, polyethers, polycarbonates, and the like comprising these as constituent components. It is done.
- dicarboxylic acid examples include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid.
- polyhydric alcohol aromatic polyhydric alcohols such as those obtained by addition reaction of bisphenol with ethylene oxide, ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, glycerin, sorbitan, trimethylolpropane
- aromatic polyhydric alcohols such as those obtained by addition reaction of bisphenol with ethylene oxide, ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, glycerin, sorbitan, trimethylolpropane
- aliphatic polyhydric alcohols such as neopentyl glycol, ether glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol.
- examples of the hydroxycarboxylic acid include glycolic acid, hydroxybutyric acid, hydroxybutylcarboxylic acid, hydroxypentanoic acid, hydroxycaproic acid, and hydroxyheptanoic acid.
- lactone acid examples include glycolide, ⁇ -caprolactone glycolide, ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, pivalolactone, ⁇ -valerolactone, and the like.
- the polylactic acid resin used in the present invention is not particularly limited in the synthesis method, and can be synthesized by a conventionally known method. For example, direct dehydration condensation from a lactic acid monomer or ring-opening polymerization of a lactic acid cyclic dimer lactide. Can be synthesized.
- any lactic acid of L-lactic acid, D-lactic acid, DL-lactic acid, and a mixture thereof may be used.
- any lactide of L-lactide, D-lactide, DL-lactide, meso-lactide, and a mixture thereof may be used.
- the catalyst used for the polymerization reaction for obtaining the polylactic acid resin is not particularly limited, but a known catalyst for lactic acid polymerization can be used.
- catalysts include tin lactate, tin tartrate, dicaprylate, dilaurate, tin dipalmitate, tin distearate, tin dioleate, ⁇ -naphthoate, ⁇ -naphthoate, and octylate.
- Tin compounds such as powder tin, tin oxide, zinc dust, zinc halide, zinc oxide, organic zinc compounds, titanium compounds such as tetrapropyl titanate, zirconium compounds such as zirconium isopropoxide, antimony trioxide, etc. Examples thereof include antimony compounds, bismuth compounds such as bismuth (III) oxide, and aluminum compounds such as aluminum oxide and aluminum isopropoxide.
- a catalyst made of tin or a tin compound is particularly preferable from the viewpoint of activity.
- the amount of the catalyst used is, for example, about 0.001 to 5 parts by mass with respect to 100 parts by mass of lactide when ring-opening polymerization is performed.
- the polymerization reaction is usually carried out at 100 to 220 ° C. in the presence of the above catalyst, although it varies depending on the type of catalyst. It is also preferable to carry out the two-stage polymerization described in, for example, JP-A-7-247345.
- the blend polymer mainly composed of the polylactic acid resin includes, for example, a polylactic acid homopolymer and / or a polylactic acid copolymer and an aliphatic polyester other than polylactic acid (hereinafter simply referred to as “aliphatic polyester”). Examples thereof include a mixture obtained by mixing and melting. Blending the aliphatic polyester is preferable because flexibility and impact resistance can be imparted to the molded product.
- the mixing ratio in the blend polymer is usually about 10 to 100 parts by mass of the aliphatic polyester with respect to 100 parts by mass of the polylactic acid homopolymer and / or polylactic acid copolymer.
- the aliphatic polyester may be a single polymer or a composite of two or more polymers.
- examples of such a polymer include a polymer composed of an aliphatic carboxylic acid and an aliphatic alcohol, and an aliphatic hydroxycarboxylic acid polymer obtained by ring-opening polymerization of a cyclic anhydride such as ⁇ -caprolactone.
- Examples of a method for obtaining these polymers include a direct polymerization method for directly polymerizing to obtain a high molecular weight product, and an indirect polymerization method for obtaining a high molecular weight product with a chain extender after polymerization to the extent of an oligomer.
- the aliphatic polyester may be a copolymer or a mixture with other resins as long as it is a polymer mainly composed of the aliphatic monomer component.
- the aliphatic polyester is preferably a polymer composed of an aliphatic dicarboxylic acid and an aliphatic diol.
- the aliphatic dicarboxylic acid include succinic acid, adipic acid, suberic acid, sebacic acid, dodecanoic acid, and anhydrides and derivatives thereof.
- the aliphatic diol include glycol compounds such as ethylene glycol, butanediol, hexanediol, octanediol, and cyclohexanedimethanol, and derivatives thereof.
- aliphatic dicarboxylic acids and aliphatic diols are preferably monomers having 2 to 10 carbon atoms or cycloalkylene.
- the aliphatic polyester is preferably produced by polycondensation of monomer components selected from each of these aliphatic dicarboxylic acids and aliphatic diols. Further, two or more of the aliphatic dicarboxylic acids and the aliphatic diols may be used.
- a trifunctional or higher polyfunctional carboxylic acid, alcohol or hydroxycarboxylic acid is used as a monomer component constituting the polymer. May be.
- these polyfunctional monomer components are used in a large amount, the resulting polymer has a cross-linked structure and may not be thermoplastic, or even a thermoplastic may produce a microgel partially having a highly cross-linked structure. . Therefore, these polyfunctional monomer components are used in such a small amount that they do not greatly affect the chemical and physical properties of the polymer.
- the polyfunctional monomer component malic acid, tartaric acid, citric acid, trimellitic acid, pyromellitic acid, pentaerythritol, trimethylolpropane, or the like can be used.
- the direct polymerization method selects a monomer component, and removes water contained in the monomer component or generated during the polymerization, while removing a high molecular weight product. How to get.
- a monomer component is selected, polymerized to an oligomer level, and then a small amount of chain extender such as hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, etc. for the purpose of increasing molecular weight.
- chain extender such as hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, etc.
- This is a method of increasing the molecular weight using a diisocyanate compound.
- a method of obtaining an aliphatic polyester carbonate using a carbonate compound may be used.
- the lactic acid-based polymer may be blended with a general-purpose resin other than the lactic acid-based polymer, if necessary, for improving impact strength.
- a general-purpose resin an elastic resin such as ethylene-propylene copolymer rubber and ethylene-propylene-diene copolymer is preferable.
- the alkyl group having 1 to 4 carbon atoms represented by R 1 , R 2 , R 3 and R 4 in the general formula (1) includes methyl group, ethyl group, propyl Group, isopropyl group, n-butyl group, secondary butyl group, tertiary butyl group and the like.
- examples of the alkyl group having 1 to 18 carbon atoms represented by R in the general formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Secondary butyl group, tertiary butyl group, isobutyl group, amyl group, isoamyl group, tertiary amyl group, hexyl group, 2-hexyl group, 3-hexyl group, heptyl group, 2-heptyl group, 3-heptyl group, Isoheptyl group, tertiary heptyl group, n-octyl group, isooctyl group, tertiary octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, undecyl group, dodecyl group
- examples of the alkyl group having 1 to 18 carbon atoms substituted by the hydroxyl group represented by R in the general formula (1) include, for example, 2-hydroxyethyl group, 2-hydroxypropyl And groups corresponding to the above alkyl groups such as a group, 3-hydroxypropyl group, 2-hydroxy-2-methylpropyl group and the like.
- examples of the acyl group having 1 to 18 carbon atoms represented by R in the general formula (1) include an acetyl group, a propanoyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, Examples include heptanoyl group, octanoyl group, decanoyl group, undecanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group and the like.
- examples of the cycloalkyl group having 5 to 8 carbon atoms represented by R in the general formula (1) include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. .
- the hindered amine compound having a partial structure represented by the general formula (1) used in the present invention more specifically, the following No. Examples of the compound are 1 to 8.
- the present invention is not limited by the following compounds.
- the hindered amine compound having a partial structure represented by the general formula (1) is 0.005 to 30 parts by mass, preferably 0.05, per 100 parts by mass of the polylactic acid resin. -10 parts by mass, more preferably 0.1-5 parts by mass.
- the amount of the hindered amine compound is less than 0.005 parts by mass, the effect of addition is insufficient, and when the amount is more than 30 parts by mass, a phenomenon such as the above-mentioned compound being ejected on the surface of the polylactic acid resin composition may occur. .
- additives usually used for each resin are used as necessary.
- additives include, for example, phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants, ultraviolet absorbers, other hindered amine compounds, nucleating agents, flame retardants, flame retardant aids, hydrotalcite And lubricants, fillers and the like.
- phenol-based antioxidant examples include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3 Bis (4-hydroxy-3-tert
- the amount of the phenolic antioxidant used is 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polylactic acid resin.
- sulfur-based antioxidant examples include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl and distearyl esters of thiodipropionic acid and polyols such as pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate). And ⁇ -alkyl mercaptopropionic acid esters.
- the amount of the sulfur-based antioxidant used is 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, with respect to 100 parts by mass of the polylactic acid resin.
- Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris ( Mono-, di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) -ethyl phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-di-tert-butyl) Phenyl) octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tri
- the amount of the phosphorus antioxidant used is 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polylactic acid resin.
- phenol-based and phosphorus-based antioxidants are preferably used because they prevent coloring of the polylactic acid resin.
- Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4 ′-(2 -Methacryloyloxyethoxyethoxy) benzophenone, 5-hydroxybenzophenones such as 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-tert Butyl-5-methylphenyl) -5-chlorobenzotriazole, -(2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-
- Phenyl) -1,3,5-triazines phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3,5-ditertiarybutyl-4-hydroxybenzoate, 2,4-ditertiary Such as amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate, etc.
- Nzoates substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; ethyl- ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, methyl-2-cyano And cyanoacrylates such as -3-methyl-3- (p-methoxyphenyl) acrylate.
- the amount of the ultraviolet absorber used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polylactic acid resin.
- Examples of the other hindered amine compounds include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, and 2,2,6. , 6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl -Piperidyl methacrylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, Trakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,
- the amount of the other hindered amine compound used is 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polylactic acid resin.
- nucleating agent examples include aromatic carboxylic acid metal salts such as aluminum pt-butylbenzoate and sodium benzoate, sodium bis (2,4-ditert-butylphenyl) phosphate, bis (2, 4-di-tert-butylphenyl) lithium phosphate, sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, and other acidic phosphate metal salts, dibenzylidene sorbitol, bis (methylbenzylidene) And polyhydric alcohol derivatives such as sorbitol, bis (p-ethylbenzylidene) sorbitol, disodium bicyclo [2.2.1] heptane-2,3-dicarboxylate, and the like.
- the amount of the nucleating agent used is 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, with respect to 100 parts by mass of the polylactic acid resin.
- the flame retardant examples include phosphate esters such as triphenyl phosphate, phenol, resorcinol, phosphorus oxychloride condensate, phenol, bisphenol A, 2,6-xylenol, resorcinol, phosphorus oxychloride condensate; aniline, oxy Phosphoric acid amides such as phosphorous chloride condensate, phenol, xylylenediamine oxyphosphoric chloride condensate; phosphazenes; halogen flame retardants such as decabromodiphenyl ether and tetrabromobisphenol A; melamine phosphate, piperazine phosphate, melamine pyrophosphate, Phosphorates of nitrogen-containing organic compounds such as piperazine pyrophosphate, melamine polyphosphate, piperazine polyphosphate; red phosphorus and surface-treated or microencapsulated red phosphorus; flame retardant aids such as antimony oxide and zinc
- the hydrotalcites may be natural products or synthetic products, and can be used regardless of the presence or absence of surface treatment or the presence or absence of crystal water.
- M represents an alkali metal or zinc
- x represents a number of 0 to 6
- y represents a number of 0 to 6
- z represents a number of 0.1 to 4
- p represents a valence of M.
- a basic carbonate represented by the following formula: n represents a number of 0 to 100 water of crystallization.
- the amount of the hydrotalcite used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polylactic acid resin.
- the lubricant examples include fatty acid amides such as lauryl amide, myristyl amide, stearyl amide, and behenyl amide, metal soaps such as ethylene bisstearyl amide, polyethylene wax, calcium stearate, and magnesium stearate, distearyl phosphate magnesium, Examples thereof include phosphate metal salts such as stearyl phosphate magnesium.
- the amount of the lubricant used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polylactic acid resin.
- the filler examples include inorganic substances such as talc, silica, calcium carbonate, glass fiber, potassium titanate, potassium borate, etc., particle diameter in the case of spherical substances, fiber diameter and fiber length in the case of fibrous substances.
- the aspect ratio is appropriately selected and used.
- the amount of the filler used is preferably 0.1 to 100 parts by mass, more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the polylactic acid resin.
- additives that are usually used as necessary, for example, coloring agents, crosslinking agents, antistatic agents, plate-out prevention agents, surface treatment agents, fluorescent agents, antifungal agents, bactericides, Metal soaps, metal deactivators, mold release agents, pigments, dyes, processing aids, foaming agents and the like can be used.
- a method of adding to the polylactic acid resin separately from the hindered amine compound having a partial structure represented by the general formula (1) used in the present invention a method of adding to the polylactic acid resin separately from the hindered amine compound having a partial structure represented by the general formula (1) used in the present invention. Or after mixing the hindered amine compound having the partial structure represented by the general formula (1) with a binder, wax, solvent, granulation aid such as silica, etc. used as necessary, in a desired ratio in advance.
- a method of granulating into a one-pack composite additive, adding the one-pack composite additive to a polylactic acid resin, and the other additive containing a hindered amine compound having a partial structure represented by the general formula (1) A method for preparing a master batch to be contained and adding it to a polylactic acid resin can be used.
- the resin molded product of the present invention is obtained by molding the above-mentioned polylactic acid resin composition, thereby providing excellent weather resistance, and unlike conventional molded products using a polylactic acid resin composition, crystallization is achieved. It does not have the problem of white turbidity.
- the method of molding the resin composition can be appropriately selected depending on the application, and is not particularly limited. For example, injection molding, extrusion molding, coextrusion molding, blow molding, press molding, cast molding, roll molding. And vacuum forming.
- the use of the resin molded product of the present invention is not particularly limited.
- building materials such as window frames, personal computer housing parts and housings, mobile phone housing parts and housings, other office equipment housing parts and housings, home appliance housing parts, and Resin parts for electrical appliances such as housings, automotive resin parts such as bumpers, spoilers, side visors, dashboards, glove boxes, console boxes, radiator grills, aero parts, instrument panels, ceilings, doors, seats, trunk rooms, etc. Is mentioned.
- it can also be set as a film, a sheet
- Example 1 Comparative Examples 1 to 3
- Polylactic acid resin LACEA H-100; manufactured by Mitsui Chemicals, Inc.
- 0.375 mg of a hindered amine compound described in Table 1 below were added to a 25 ml volumetric flask and diluted with methylene chloride. 4 ml of the resulting solution was placed in a petri dish and the solvent was removed to prepare a cast film test piece having a thickness of 70 to 90 ⁇ m. The evaluation shown below was implemented using the obtained test piece.
- Example 4 Based on the formulation described in Table 1 below, a test piece was prepared in the same manner as in Example 1 and Comparative Examples 1 to 3 except that no hindered amine compound was added, and the weather resistance was evaluated. The results are shown in Table 1 below.
- the polylactic acid resin composition of Example 1 using the hindered amine compound having the partial structure represented by the general formula (1) is the same as that of Comparative Examples 1 to 3 using conventional hindered amine compounds. Compared to the polylactic acid resin composition, it has been confirmed that it has excellent weather resistance and also has an effect of suppressing crystallization of the polylactic acid resin.
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Abstract
Description
(式中、R1、R2、R3およびR4は各々独立に炭素原子数1~4のアルキル基を表し、Rは水酸基で置換されていてもよい炭素原子数1~18のアルキル基、炭素原子数1~18のアシル基、または炭素原子数5~8のシクロアルキル基を表す)で表される部分構造を有するヒンダードアミン化合物0.005~30質量部が配合されてなることを特徴とするものである。
(式中、Rは前記一般式(1)と同じものを表す)で表される化合物であることが好ましい。
本発明において用いられるポリ乳酸樹脂としては、ポリ乳酸ホモポリマー、ポリ乳酸コポリマー、ポリ乳酸ホモポリマーとポリ乳酸コポリマーとのブレンドポリマーが挙げられる。また、本発明の効果を損なわない範囲であれば、ポリ乳酸を主体とするブレンドポリマーであってもよい。
MxMgyAlzCO3(OH)xp+2y+3z-2・nH2O (3)
(式中、Mはアルカリ金属または亜鉛を表し、xは0~6の数を表し、yは0~6の数を表し、zは0.1~4の数を表し、pはMの価数を表し、nは0~100の結晶水の数を表す)で表される塩基性炭酸塩が挙げられる。上記ハイドロタルサイト類の使用量は、ポリ乳酸樹脂100質量部に対して、好ましくは0.001~10質量部、より好ましくは0.01~5質量部である。
ポリ乳酸樹脂(LACEA H-100;三井化学株式会社製)1.25gおよび下記表1中に記載のヒンダードアミン化合物0.375mgを25mlメスフラスコに加え、塩化メチレンでメスアップした。得られた溶液4mlをシャーレに入れ、溶媒を除去することにより、厚みが70~90μmのキャストフィルムの試験片を作製した。得られた試験片を用いて、下記に示す評価を実施した。
得られた試験片の耐候性の評価として、スガ試験機株式会社製サンシャイン・カーボンアーク・ウェザーメーター(ブラックパネル温度63℃、120分中に18分間水スプレー有り)にて、120時間毎に試験片表面を観察し、試験片表面にクラックが発生した時間を求めた。その結果を下記表1中に示す。
得られた試験片の結晶化状態について、上記耐候試験中の試験片を360時間毎に取り出して、試験片のHaze(ヘイズ)(%)値で評価した。なお、試験片の結晶化が進むと、ヘイズの値が高くなり試験片は白濁化する。その結果を下記表1中に示す。
下記表1中に記載の配合に基づき、ヒンダードアミン化合物を添加しない以外は上記実施例1および比較例1~3と同様の方法で試験片を作製して、耐候性評価を行った。その結果を下記表1中に示す。
Claims (4)
- 請求項1記載のポリ乳酸樹脂組成物が成形加工されてなることを特徴とする樹脂成形品。
- 請求項2記載のポリ乳酸樹脂組成物が成形加工されてなることを特徴とする樹脂成形品。
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EP09714710.2A EP2253667B1 (en) | 2008-02-29 | 2009-02-16 | Use of a polylactic acid resin molded article for building materials |
CN2009801056694A CN101945947A (zh) | 2008-02-29 | 2009-02-16 | 聚乳酸树脂组合物 |
US12/919,784 US8293824B2 (en) | 2008-02-29 | 2009-02-16 | Polylactic acid resin composition |
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EP (3) | EP2749598B1 (ja) |
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CN1926107B (zh) * | 2004-03-02 | 2012-01-04 | 株式会社艾迪科 | 具有碳酸酯骨架的弱碱性受阻胺类化合物、合成树脂组合物和涂料组合物 |
WO2011127462A2 (en) | 2010-04-09 | 2011-10-13 | E Ink Corporation | Methods for driving electro-optic displays |
BR112013019008B1 (pt) * | 2011-01-25 | 2020-04-07 | Sk Chemicals Co Ltd | película de resina de ácido poliláctico |
WO2013123364A1 (en) | 2012-02-17 | 2013-08-22 | Andersen Corporation | Polylactic acid containing building component |
WO2015061760A1 (en) * | 2013-10-24 | 2015-04-30 | Clearsign Combustion Corporation | System and combustion reaction holder configured to transfer heat from a combustion reaction to a fluid |
US10268066B2 (en) * | 2015-01-09 | 2019-04-23 | Samsung Display Co., Ltd. | Photosensitive resin composition, color conversion panel using the same and display device |
KR102133297B1 (ko) | 2018-12-10 | 2020-07-13 | 엘지엠엠에이 주식회사 | 생분해성 필름 조성물 |
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Also Published As
Publication number | Publication date |
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JP5420179B2 (ja) | 2014-02-19 |
EP2253667A1 (en) | 2010-11-24 |
JP2009209177A (ja) | 2009-09-17 |
KR20100126770A (ko) | 2010-12-02 |
EP2749598B1 (en) | 2016-08-24 |
EP2253667A4 (en) | 2013-05-22 |
US8293824B2 (en) | 2012-10-23 |
EP2253667B1 (en) | 2015-03-25 |
KR101545932B1 (ko) | 2015-08-20 |
EP2749599A1 (en) | 2014-07-02 |
CN101945947A (zh) | 2011-01-12 |
EP2749598A1 (en) | 2014-07-02 |
US20110003917A1 (en) | 2011-01-06 |
EP2749599B1 (en) | 2016-09-21 |
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