JP2005226055A - Aliphatic polyester resin molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aliphatic polyester resin molded product which is biodegradable and satisfies both high impact resistance and heat resistance. <P>SOLUTION: The aliphatic polyester resin molded product is composed of a resin composition mainly composed of an aliphatic polyester and has a Charpy impact strength at 25&deg;C of 15-230 kJ/m<SP>2</SP>and a heat distortion temperature under a load of 0.45 MPa of 100-170&deg;C. <P>COPYRIGHT: (C)2005,JPO&amp;NCIPI

Description

  The present invention relates to an aliphatic polyester resin molded article that is biodegradable and has both high impact resistance and heat resistance.

In recent years, biodegradable polymers that are decomposed by microorganisms and the like have attracted attention with increasing social demand for protection of the global environment.
Specific examples of biodegradable polymers include those that can be melt-molded such as aliphatic polyesters such as polybutylene succinate, polycaprolactone, and polylactic acid, and copolymers of terephthalic acid / 1,4-butanediol / adipic acid. Examples include polyester. Among these aliphatic polyesters, polylactic acid, which is widely distributed in nature and harmless to animals, plants and animals, has a melting point of 140 to 175 ° C., has sufficient heat resistance, has high strength and is relatively inexpensive. It is expected as a thermoplastic biodegradable resin. However, the impact resistance is low and improvement is required.

As means for improving the impact resistance of polylactic acid, a method of adding a polyester-based plasticizer (for example, see Patent Documents 1 and 2), a method of adding an olefin-based or conjugated diene-based elastomer (for example, a patent) References 3 to 6) are known. However, if the plasticizer component or elastomer component is increased in order to improve the impact resistance, the impact resistance will be improved, but the heat resistance will be lowered, and if the heat resistance is to be maintained, sufficient impact resistance will be obtained. There was a problem that it was not possible.
Disclosed is a biodegradable resin composite material characterized by comprising polylactic acid and a layered clay compound that is organicized with an organic onium salt having a hydroxyl group and bonded to the polylactic acid via the hydroxyl group of the organic onium salt. However, it cannot be said that the impact resistance is sufficient, and the heat resistance is not described (for example, refer to Patent Document 7).

A technique relating to a polylactic acid composite material containing a low molecular weight compound having an amide group and a layered clay mineral organized with an organic onium salt is disclosed, and a test piece injection-molded at a mold temperature of 120 ° C. and a cooling time of 120 sec. However, there is no description about impact resistance (for example, refer patent document 8).
Although a molded product in which a hydrolysis inhibitor is added to an aliphatic polyester resin composition part having a glass transition temperature of 0 ° C. or less is described in polylactic acid, it cannot be said that sufficient impact resistance is shown ( For example, see Patent Document 9.)
Although a composition containing a whisker in a lactic acid-based polymer and a molded product thereof are described, it cannot be said that sufficient impact resistance is exhibited (for example, see Patent Document 10).

Layered silicate having a biodegradable polyester resin containing 50 parts by weight or more of polylactic acid having a D-form content of 2% by weight or less and a primary to tertiary amine salt, quaternary ammonium salt, or phosphonium salt between layers A biodegradable resin composition characterized by having a heat deformation temperature of 90 ° C. or higher at a load of 0.98 MPa is disclosed, and an example of a heat deformation temperature of 100 ° C. or higher at a load of 0.98 MPa is disclosed. Although described, there is no description about impact resistance (for example, refer patent document 11).
An aliphatic polyester resin composition containing an aliphatic polyester containing polylactic acid and a multilayer structure polymer is disclosed, and a molded article excellent in impact resistance molded at a mold temperature of 40 ° C., and further a crystal nucleating agent A molded product having a heat deformation temperature exceeding 100 ° C. at a load of 0.45 MPa formed by adding a filler and a plasticizer and molding at a mold temperature of 80 ° C. is exemplified. However, as in the present invention, a molded article having a Charpy impact strength at 25 ° C. of 15 kJ / m ² or more and a thermal deformation temperature of 100 ° C. or more at a load of 0.45 Pa is not disclosed (for example, Patent Document 12). reference.).

JP-A-8-283557 JP 2002-327107 A Japanese Patent No. 3390855 JP 2000-95898 A JP 2000-219803 A JP 2001-123055 A JP 2003-73538 A JP 2003-226801 A JP 2002-309074 A JP 2003-231799 A JP 2003-261756 A JP 2003-286396 A

  The present invention is intended to solve the above-described problems, and provides a molded article that is biodegradable and has both excellent impact resistance and heat resistance.

The present inventor has found that the molded product obtained from the aliphatic polyester resin composition has excellent impact resistance and heat resistance, as a result of intensive studies to solve the above problems, The present invention has been completed.
That is, the present invention
1. It consists of a resin composition mainly composed of an aliphatic polyester resin, and has a Charpy impact strength at 25 ° C. of 15 to 230 kJ / m ² and a heat deformation temperature of 100 to 170 ° C. under a load of 0.45 MPa. Aliphatic polyester resin molding,
2. 2. The aliphatic polyester resin molded article according to 1 above, wherein the aliphatic polyester resin composition comprises an aliphatic polyester resin (A) and an elastomer (B),

3. (B) The aliphatic polyester resin composition according to the above 1 or 2, wherein the component is a modified conjugated diene copolymer,
4). (B) Modified conjugated diene polymer wherein the component is modified with a compound having at least one polar group selected from an amino group, an imino group, a hydroxyl group, an epoxy group, a carboxyl group and an acid anhydride group The aliphatic polyester resin composition according to any one of the above 1 to 3, wherein

5). (B) A modified conjugate in which the component is a compound having at least one polar group selected from an amino group, an imino group, a hydroxyl group, an epoxy group, a carboxyl group, and an acid anhydride group, the terminal of which is modified The aliphatic polyester resin composition according to any one of the above 1 to 4, which is a diene polymer,
6). (B) The aliphatic polyester resin molded article according to any one of 1 to 5 above, wherein the component is a modified conjugated diene copolymer modified with a compound having an imidazolidinone skeleton,
7). The aliphatic polyester resin composition according to any one of the above 1 to 6, wherein the aliphatic polyester resin composition comprises (C) a crystal nucleating agent,
It is.

  The molded article of the present invention is a molded article that is biodegradable and has both excellent impact resistance and heat resistance.

Hereinafter, the present invention will be specifically described.
The (a) aliphatic polyester of the present invention is not particularly limited, and is a polymer mainly composed of an aliphatic hydroxycarboxylic acid, and mainly composed of an aliphatic polycarboxylic acid and an aliphatic polyhydric alcohol. And the like. Specifically, polymers having aliphatic hydroxycarboxylic acid as a main component include polyglycolic acid, polylactic acid, poly-3-hydroxybutyric acid, poly-4-hydroxybutyric acid, poly-4-hydroxyvaleric acid, poly-3- Hydroxyhexanoic acid or polycaprolactone, etc., and examples of the polymer mainly composed of aliphatic polycarboxylic acid and aliphatic polyhydric alcohol include polyethylene adipate, polyethylene succinate, polybutylene adipate, or polybutylene succinate. Is mentioned. These aliphatic polyesters can be used alone or in combination of two or more. Among these aliphatic polyesters, a polymer containing hydroxycarboxylic acid as a main constituent is preferable, and a polylactic acid resin is particularly preferably used. These (a) components can use 1 or more types.

  The polylactic acid-based resin of the present invention is polylactic acid, a lactic acid-hydroxycarboxylic acid copolymer, and a mixture of polylactic acid and lactic acid-hydroxycarboxylic acid copolymer, and has a lactic acid ratio in the polymer of 75% by weight or more. As the polymer raw material, lactic acid and hydroxycarboxylic acid are used. As lactic acid, L-lactic acid, D-lactic acid, DL-lactic acid or a mixture thereof or lactide which is a cyclic dimer of lactic acid can be used. These lactic acids can be used in various combinations such that the L-lactic acid content in the obtained L-lactic acid polymer is 75% by weight or more. Examples of hydroxycarboxylic acids that can be used in combination with lactic acids include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, and 6-hydroxycaproic acid. Cyclic dimers such as glycolide, which is a dimer of glycolic acid, or cyclic ester intermediates such as ε-caprolactone can also be used.

  The polylactic acid resin used in the present invention is made from lactic acid having an L-lactic acid content of 75% by weight or more as a raw material, or a mixture of lactic acid and hydroxycarboxylic acid, and the L-lactic acid content in the mixture is 75% by weight. Direct dehydration polycondensation using the mixture prepared as described above as a raw material, or a cyclic dimer of lactide or hydroxycarboxylic acid, for example, a dimer of glycolic acid, which is a cyclic dimer of lactic acid. It can be obtained by a ring-opening polymerization method using a cyclic ester intermediate such as glycolide or ε-caprolactone.

  In the case of producing by direct dehydration condensation, the raw material lactic acid or lactic acid and hydroxycarboxylic acid are preferably subjected to azeotropic dehydration condensation in the presence of an organic solvent, particularly a phenyl ether solvent, and particularly preferably a solvent distilled by azeotropic distillation. Polymerization is performed by a method in which water is removed from the solvent and the solvent is brought into a substantially anhydrous state and returned to the reaction system to obtain a high molecular weight polylactic acid resin having strength suitable for the present invention. The weight average molecular weight of the polylactic acid-based resin is preferably a high molecular weight within the range that can be molded, and more preferably 30,000 or more. If the weight average molecular weight is less than 30,000, the strength of the molded product may be reduced and may not be suitable for practical use. Even if the weight average molecular weight is 1,000,000 or more, it can be used for the production of the molded product of the present invention if the moldability is devised. Further, if the weight average molecular weight exceeds 5 million, the moldability may be inferior.

The elastomer (B) that can be used in the present invention is preferably at least one selected from a modified conjugated diene polymer, a modified olefin polymer, and a multilayer structure polymer, or a combination thereof.
The modified conjugated diene polymer preferably used in the present invention has at least one or two or more polar groups selected from an amino group, an imino group, a hydroxyl group, an epoxy group, a carboxyl group, and an acid anhydride group. It is a conjugated diene polymer characterized by being modified with a compound. Here, the conjugated diene polymer is a homopolymer of conjugated diene, a copolymer of conjugated diene and vinyl aromatic hydrocarbon, or a hydrogenated product thereof. The polymer conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Among them, one or more kinds can be used, and 1,3-butadiene, isoprene or a combination thereof is generally preferred.

  The aromatic vinyl compound is one of styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene and the like. Alternatively, two or more types can be used, and styrene is generally preferable. The content of the aromatic vinyl compound in the copolymer is 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less. If it exceeds 50% by weight, the effect of imparting impact resistance is insufficient, which is not preferable. Both units may be copolymerized randomly, copolymerized in blocks, or a copolymer containing random copolymerized blocks, but preferably, for example, mainly composed of vinyl aromatic hydrocarbons. It is a block copolymer comprising at least one polymer block A and at least one polymer block B mainly composed of conjugated diene, or a hydrogenated product thereof. More preferably, it is a block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and one polymer block B mainly composed of conjugated diene.

  Examples of the method for producing a copolymer of a conjugated diene polymer and a vinyl aromatic hydrocarbon used in the present invention include Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-171979, and Japanese Patent Publication No. 46-. No. 32415, JP-B 49-36957, JP-B 48-2423, JP-B 48-4106, JP-B 56-28925, JP-B 51-49567, JP-A 59-166518 And the methods described in JP-A-60-186577 and the like. The block copolymer obtained by these methods has, for example, a structure represented by the following general formula (for a hydrogenated product, a polymer structure before hydrogenation).

(AB) _n , (BA) _n , A- (BA) _n , B- (AB) _n ,
[(BA) _n ] _m -X, [(AB) _n ] _m X,
[(BA) _n -B] _m -X, [(AB) _n -A] _m -X
(In the above formula, A is a polymer block mainly composed of vinyl aromatic hydrocarbons, and B is a polymer block mainly composed of conjugated dienes. X is a residue of a coupling agent or a polyfunctional organolithium compound. And n is an integer of 1 or more, generally an integer of 1 to 5, and m is an integer of 2 or more, generally an integer of 2 to 10.)

  In the above, the polymer block A mainly composed of vinyl aromatic hydrocarbon is preferably a vinyl aromatic hydrocarbon containing 50% by weight or more, more preferably 70% by weight or more of vinyl aromatic hydrocarbon and conjugated diene. The copolymer block or / and the vinyl aromatic hydrocarbon homopolymer block, and the polymer block B mainly composed of a conjugated diene is preferably an amount exceeding 50% by weight, more preferably 60%. A copolymer block of a conjugated diene and a vinyl aromatic hydrocarbon or / and a conjugated diene homopolymer block containing at least% by weight is shown. The vinyl aromatic hydrocarbons in the copolymer block may be distributed uniformly or in a tapered shape. In the copolymer block, a plurality of portions where the vinyl aromatic hydrocarbons are uniformly distributed and / or a portion where they are distributed in a tapered shape may coexist.

  In the present invention, examples of the solvent used for the production of the conjugated diene polymer include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, and isooctane, cyclopentane, methylcyclopentane, cyclohexane, and methyl. Cycloaliphatic hydrocarbons such as cyclohexane and ethylcyclohexane or aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene can be used. These may be used alone or in combination of two or more.

  In the present invention, the organolithium compound used as a polymerization initiator in the production of a conjugated diene polymer is a compound in which one or more lithium atoms are bonded in the molecule, for example, ethyl lithium, n-propyl lithium, isopropyl Lithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexamethylenedilithium, butadienyldilithium, isoprenyldilithium and the like can be used. These may be used alone or in combination of two or more. The organolithium compound may be added in one or more divided portions during the polymerization in the production of the block copolymer.

  In the present invention, for the purpose of controlling the polymerization rate during production of the conjugated diene polymer, controlling the microstructure of the polymerized conjugated diene moiety, controlling the reactivity ratio between the vinyl aromatic hydrocarbon and the conjugated diene, Randomizing agents can be used. Examples of polar compounds and randomizing agents include ethers, amines, thioethers, phosphines, phosphoramides, potassium or sodium salts of alkylbenzene sulfonic acids, potassium or sodium alkoxides, and the like. Specific examples of the ethers include dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether. Examples of amines include tertiary amines, trimethylamine, triethylamine, tetramethylethylenediamine, and other cyclic tertiary amines. Examples of phosphine and phosphoramide include triphenylphosphine and hexamethylphosphoramide.

In the present invention, the polymerization temperature for producing the conjugated diene polymer is preferably 10 to 150 ° C, more preferably 30 to 120 ° C.
The polymerization time varies depending on the conditions, but is preferably within 48 hours, particularly preferably 0.5 to 10 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is within a range sufficient to maintain the monomer and solvent in a liquid phase within the above polymerization temperature range. Furthermore, it is preferable to pay attention so that impurities that inactivate the catalyst and the living polymer, for example, water, oxygen, carbon dioxide gas, and the like are not mixed in the polymerization system.

The modified conjugated diene copolymer (B) used in the present invention is at least one or two or more polar groups selected from an amino group, an imino group, a hydroxyl group, an epoxy group, a carboxyl group, and an acid anhydride group. A modified conjugated diene polymer characterized by being modified with a compound having an amino acid group, and particularly preferred polar groups are amino groups and / or imino groups. By using the modified conjugated diene copolymer having such a polar group, the effect of improving the impact resistance of the polylactic acid resin becomes very remarkable.
The modified conjugated diene polymer has a functional group related to the polymer block A and / or the polymer block B, or a polymer in which an atomic group having a functional group related to the polymer of the conjugated diene is bonded to the terminal. The aforementioned block copolymer having an atomic group bonded to the terminal (hereinafter referred to as a modified block copolymer) is particularly preferred. The structure of the modified block copolymer is represented by the following general formula, for example.

(AB) _n -Y, (BA) _n -Y,
A- (BA) _n -Y, B- (AB) _n -Y,
Y- (AB) _n -Y, YA- (BA) _n -Y,
Y-B- (AB) _n -Y,
_{[(B-A) n]} m -Y, [(A-B) n] m -Y,
[(BA) n-B] _m- Y, [(AB) _n- A] _m- Y
(In the above formula, A is a polymer block mainly composed of vinyl aromatic hydrocarbon, B is a polymer block mainly composed of conjugated diene, and n is an integer of 1 or more, generally 1-5. And m is an integer of 2 or more, generally an integer of 2 to 10. Y is a modifier residue to which an atomic group having a functional group described below is bonded.
The modified block copolymer used in the present invention may be any mixture of modified block copolymers represented by the above general formula.

  A method for obtaining a modified conjugated diene polymer is such that a modifying agent in which a functional group having a functional group is bonded to the living end of the conjugated diene polymer or an atomic group in which the functional group is protected by a known method is bonded. And a method of reacting the modifying agent. Depending on the type of modifier, the hydroxyl group or amino group may be an organometallic salt at the stage of reaction of the modifier, but in that case, treatment with a compound having active hydrogen such as water or alcohol is required. Can be converted into a hydroxyl group or an amino group. In the present invention, after the modifier is reacted with the living terminal of the conjugated diene polymer, a part of the conjugated diene polymer that is not modified may be mixed. The proportion of the unmodified conjugated diene polymer mixed in the modified conjugated diene polymer is preferably 70% by weight or less, more preferably 60% by weight or less, and still more preferably 50% by weight or less.

  In the present invention, a silanol group, an alkoxy, which can be used to obtain a modified conjugated diene copolymer modified with an amino group, an imino group, a hydroxyl group, an epoxy group, and a carboxyl group and an acid anhydride group described later. Examples of the atomic group having at least one functional group selected from silane include atomic groups selected from the following general formula.

(In the above formula, R ⁹ and R ^{12 to} R ¹⁴ are each a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, or a carbon group having a functional group selected from a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilane. the hydrocarbon group ^{.R 10} of 24 hydrocarbon chain having 1 to 30 carbon atoms or a hydroxyl group, a hydrocarbon chain having 1 to 30 carbon atoms having an epoxy group, a silanol group, a functional group selected from alkoxysilane. Note ^{R 9} And the hydrocarbon group of R ^{12 to} R ¹⁴ and the hydrocarbon chain of R ¹⁰ are bonded with elements such as oxygen, nitrogen, silicon and the like in a bonding mode other than a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilane. R ¹¹ is hydrogen or an alkyl group having 1 to 8 carbon atoms.)

  In the present invention, a silanol group, an alkoxysilane, which can be used to obtain a conjugated diene copolymer modified with an amino group, an imino group, a hydroxyl group, an epoxy group, and a carboxyl group and an acid anhydride group described later Examples of the modifier used to obtain a conjugated diene polymer having at least one atomic group having at least one functional group selected from the following groups are listed below.

  For example, tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidylorthotoluidine, γ-glycidoxyethyltrimethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxy Examples include silane.

  Also, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyl Diethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycyl Sidoxypropyldiethylethoxysilane and γ-glycidoxypropyldimethylethoxysilane are exemplified.

  Also, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropylmethyldiisopropeneoxysilane, bis (γ-glycidoxypropyl) dimethoxysilane, bis (γ -Glycidoxypropyl) diethoxysilane, bis (γ-glycidoxypropyl) dipropoxysilane, bis (γ-glycidoxypropyl) dibutoxysilane, bis (γ-glycidoxypropyl) diphenoxysilane, bis (Γ-glycidoxypropyl) methylmesisilane and bis (γ-glycidoxypropyl) methylethoxysilane are mentioned.

  Also, bis (γ-glycidoxypropyl) methylpropoxysilane, bis (γ-glycidoxypropyl) methylbutoxysilane, bis (γ-glycidoxypropyl) methylphenoxysilane, tris (γ-glycidoxypropyl) Methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, bis (γ-methacryloxypropyl) dimethoxysilane, Examples include tris (γ-methacryloxypropyl) methoxysilane, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyl-triethoxysilane.

  Β- (3,4-epoxycyclohexyl) ethyl-tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane, β- (3,4-epoxycyclohexyl) ethyl-triphenoxysilane, β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldimethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyl-ethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane, β- (3,4-epoxycyclohexyl) ethyl- It includes chill dibutoxy silane.

  Β- (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylethoxysilane Β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylbutoxysilane, β -(3,4-epoxycyclohexyl) ethyl-dimethylphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane, 1,3-dimethyl-2 Imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea, N-methylpyrrolidone, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl)- 1-propanamine etc. are mentioned. Among these, 1,3-dimethyl-2-imidazolidinone and / or 1,3-diethyl-2-imidazolinone is preferable.

  By reacting the above modifier, a conjugated diene polymer (polymer block A and / or polymer block B in the case of a block copolymer) is added to a hydroxyl group, an epoxy group, an amino group, an imino group, a silanol group, an alkoxy group. A conjugated diene polymer having at least one residue of a modifying agent to which an atomic group having at least one functional group selected from silanes is bonded or a hydrogenated product thereof is obtained. The position where the residue of the modifier is bonded to the modified block copolymer is not particularly limited, but is preferably bonded to the polymer block A in order to obtain a composition having excellent physical properties at high temperatures.

  In the present invention, a hydrogenated product of a conjugated diene polymer is obtained by hydrogenating a conjugated diene polymer (in the case of a block copolymer, the block copolymer obtained above). The hydrogenation catalyst used in the case of hydrogenation is not particularly limited, and is conventionally known (1) supported by supporting a metal such as Ni, Pt, Pd, Ru on carbon, silica, alumina, diatomaceous earth, or the like. Type heterogeneous catalyst, (2) so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr, or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum, (3) A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Ti, Ru, Rh, or Zr is used. Specific examples of the hydrogenation catalyst include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-337970, Japanese Patent Publication No. 1-53851, The hydrogenation catalyst described in Japanese Patent Publication No. 2-9041 can be used. Preferable hydrogenation catalysts include a mixture with a titanocene compound and / or a reducing organometallic compound.

As the titanocene compound, a compound described in JP-A-8-109219 can be used. Specific examples thereof include (substituted) cyclohexane such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Examples thereof include compounds having at least one ligand having a pentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton. Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.
The hydrogenation reaction is generally carried out in the temperature range of 0 to 200 ° C, preferably 30 to 150 ° C. The pressure of hydrogen used in the hydrogenation reaction is 0.1 to 15 MPa, preferably 0.2 to 10 MPa, and more preferably 0.3 to 5 MPa. The hydrogenation reaction time is 3 minutes to 10 hours, preferably 10 minutes to 5 hours. For the hydrogenation reaction, any of a batch process, a continuous process, or a combination thereof may be used.

In the hydrogenated product of the modified conjugated diene polymer used in the present invention, the hydrogenation rate of the unsaturated double bond based on the conjugated diene can be arbitrarily selected according to the purpose. When obtaining a hydrogenated vinyl aromatic hydrocarbon elastomer having good thermal stability and weather resistance, more than 70%, preferably 75% or more of the unsaturated double bonds based on the conjugated diene compound in the polymer. It is recommended that 85% or more, particularly preferably 90% or more, be hydrogenated.
The hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the copolymer is not particularly limited, but the hydrogenation rate is 50% or less, preferably 30% or less, more preferably 20%. The following is preferable. The hydrogenation rate can be known by a nuclear magnetic resonance apparatus (NMR).

The weight average molecular weight of the modified conjugated diene polymer used in the present invention is preferably 30,000 or more from the viewpoint of the impact strength improving effect of the composition, and preferably 1,000,000 or less, more preferably 60,000 to 800,000 from the viewpoint of workability. More preferably, it is 70 to 600,000. The weight average molecular weight is measured by gel permeation chromatography (GPC), and a calibration curve obtained by measuring the molecular weight of the chromatogram peak from a commercially available standard polystyrene (created using the peak molecular weight of standard polystyrene) Can be determined using
When the conjugated diene polymer is a block copolymer, the content of the vinyl aromatic hydrocarbon homopolymer block is determined by oxidative decomposition using di-tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et-al., J. Polym. Sci. 1, 429 (1946)), a vinyl aromatic hydrocarbon homopolymer block component obtained by decomposing a modified block copolymer before hydrogenation (however, The amount of the component having a polymerization degree of 30 or less is removed) can be determined using an ultraviolet spectrophotometer or the like.

  The solution of the conjugated diene polymer or its hydrogenated product obtained as described above can remove the catalyst residue as needed, and separate the conjugated diene polymer or its hydrogenated product from the solution. As a method for separating the solvent, for example, a method of adding a polar solvent which is a poor solvent for a polymer such as acetone or alcohol to the polymer solution, and precipitating the polymer, collecting the polymer solution in hot water with stirring. A method of charging and removing the solvent by steam stripping and recovering, or a method of directly heating the polymer solution and distilling off the solvent can be mentioned.

  The modified olefin polymer that can be used in the present invention is, for example, a copolymer obtained by graft-reacting a (meth) acrylic ester or styrene with a copolymer of an α-olefin and an acrylic ester, and an α-olefin and acetic acid. A copolymer obtained by graft-reacting a (meth) acrylic acid ester or styrene with a vinyl copolymer, and a (meth) acrylic acid ester with a copolymer of an α-olefin and a glycidyl group-containing monomer having an ethylenically unsaturated bond. Or an epoxy group-containing olefin copolymer obtained by graft polymerization of styrene, a copolymer obtained by graft reaction of ethylene, an acrylate ester and an acid anhydride, or a copolymer obtained by grafting maleic acid to an ethylene-propylene copolymer. Such as coalescence.

  The multi-layer structure polymer that can be used in the present invention is a multi-layer structure polymer having one or more rubber layers therein, and the type of the rubber layer is not particularly limited, and a polymer having rubber elasticity. What is necessary is just to be comprised from a component. For example, a rubber component obtained by polymerizing an acrylic component, a silicon component, a styrene component, a nitrile component, a conjugated diene component, a urethane component, an ethylene propylene component, or the like can be given. The layers other than the rubber layer of the multilayer structure are not particularly limited as long as they are composed of a polymer component having thermoplasticity, but a polymer component having a glass transition point higher than that of the rubber layer is preferable. The polymer having thermoplasticity is at least one selected from unsaturated carboxylic acid alkyl ester, glycidyl machine-containing vinyl, unsaturated dicarboxylic acid and its anhydride, aliphatic vinyl, aromatic vinyl, or other vinyl-based units. Examples include polymers containing units of more than one species.

In addition, stabilizers, such as various phenol type stabilizers, phosphorus type stabilizers, sulfur type stabilizers, and amine type stabilizers, can be added to the modified conjugated diene polymer used in the present invention.
In the present invention, the method for obtaining a modified conjugated diene polymer modified with a carboxyl group or an acid anhydride group is a functional group selected from the aforementioned hydroxyl group, amino group, imino group, epoxy group, silanol group, and alkoxysilane. And a method in which a modified conjugated diene polymer having at least one atomic group having at least one is bonded with a modifier having a carboxyl group or a modifier having an acid anhydride group.

Specific examples of the modifying agent having a carboxyl group include aliphatic carboxylic acids such as maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carbaryl acid, cyclohexanedicarboxylic acid, and cyclopentanedicarboxylic acid. And aromatic carboxylic acids such as acid, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, and pyromellitic acid.
Specific examples of the modifier having an acid anhydride group include maleic anhydride, itaconic anhydride, pyromellitic anhydride, cis-4-cyclohexane-1,2-dicarboxylic anhydride, 1,2,4,5- Examples thereof include benzenetetracarboxylic dianhydride and 5- (2,5-dioxytetrahydroxyfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic-dicarboxylic anhydride.

  In addition, as another method for obtaining a modified conjugated diene polymer modified with a carboxyl group or an acid anhydride group, a conjugated diene polymer may be an α, β-unsaturated carboxylic acid or a derivative thereof such as an anhydride thereof, Examples of the method include graft modification with an esterified product, an amidated product, and an imidized product. Specific examples of α, β-unsaturated carboxylic acid or derivatives thereof include maleic anhydride, maleic anhydride imide, acrylic acid or ester thereof, methacrylic acid or ester thereof, endo-cis-bicyclo [2,2,1 ] -5-heptene-2,3-dicarboxylic acid or an anhydride thereof. The addition amount of the α, β-unsaturated carboxylic acid or derivative thereof is generally 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight per 100 parts by weight of the vinyl aromatic hydrocarbon elastomer.

The aliphatic polyester resin molding of the present invention has a Charpy impact strength at 25 ° C. of 15 to 230 kJ / m ² and a thermal deformation temperature of 100 to 170 ° C. under a load of 0.45 MPa. Preferably, the Charpy impact strength is 20 to 230 kJ / m ² and the heat distortion temperature is 110 to 170 ° C.
Further, the Charpy impact strength includes those defined in ISO 179-1 as partial break or non-break.
In order to obtain a resin composition mainly comprising the aliphatic polyester of the present invention, the blending ratio of the aliphatic polyester resin (A) and the elastomer (B) is in the range of 99.5 / 0.5 to 50/50. More preferably, it is in the range of 99/1 to 60/40, more preferably 99/2 to 50/50.

In the present invention, in order to promote crystallization of the aliphatic polyester resin composition, a crystal nucleating agent, a crystallization accelerator and the like can be blended. The crystal nucleating agent and crystallization accelerator of component (C) are not particularly limited, but include talc, silica, aromatic organophosphate metal salt compounds, dibenzylidene sorbitol compounds, fatty acid amides, plant waxes, etc. Is preferred.
The compounding amount of the crystal nucleating agent (C) is preferably in the range of 0.01 to 30 parts by weight, more preferably 0. 0 parts by weight with respect to 100 parts by weight of the total amount of the aliphatic polyester resin (A) and the elastomer (B). It is the range of 03-20 weight part.

These mixing reaction methods and mixing apparatuses can use ordinary kneading apparatuses and are not particularly limited, but those capable of continuous processing are industrially advantageous and desirable.
For example, the aliphatic polyester resin (A), the elastomer (B) and the crystal nucleating agent (C) that are preferably used may be mixed in a predetermined ratio, put into a hopper of a molding machine, melted, and immediately molded. . Moreover, after each component is melt-mixed, it may be once pelletized and then melt-molded as necessary. In order to mix uniformly, the method of once pelletizing is preferable.
The melt extrusion temperature is appropriately selected in consideration of the melting point and mixing ratio of the aliphatic polyester resin composition to be used, but is usually in the range of 100 to 250 ° C. It is preferable to select from the range of 120 to 220 ° C. The melting time is preferably within 20 minutes, and more preferably within 10 minutes.

(C) The method for adding the crystal nucleating agent is not particularly limited, but the mixture of the three components in advance as described above may be melt-mixed, and if it is a liquid substance, a fixed amount such as a plunger pump or tube pump may be used. Using a highly efficient feed pump, (A) the aliphatic polyester resin and (B) the elastomer may be added dropwise to the melt-mixed place.
In producing the aliphatic polyester resin molding of the present invention, the molding method is not particularly limited as in the case of general plastics, and injection molding, gas injection molding, extrusion molding, blow molding, inflation molding, reverent extrusion molding, injection blow molding. It can be suitably used for any of molding, vacuum / pressure forming, compression molding and the like.

In addition, in order to obtain a molded product having sufficient impact resistance and heat resistance, a melt of the resin composition is filled in a mold and crystallized as it is in the mold, or cooled and molded. After taking out the body, it is desirable to crystallize the molded article by a method of crystallizing by holding at a crystallization temperature for a certain time.
The crystallization temperature is a temperature not higher than the melting point and not lower than the glass transition point, and is in the range of about 60 ° C. to 160 ° C., preferably 70 ° C. to 130 ° C., more preferably 80 ° C. to 120 ° C.
The molded body of the present invention can be molded into various shapes by various methods, and is a film, a sheet, an injection molded body, a blow molded body, an extrusion molded body, a vacuum / pressure molded body, a laminated structure, a container, a foamed body, and a fiber. It can be used in various fields such as automobiles, electrical / electronics, packaging, agriculture, fishery, medical, and other general goods as woven and non-woven fabrics.
Specifically, in the automotive field, it can be used for interior and exterior parts such as bumpers, radiator grills, side moldings, garnishes, wheel covers, aero parts, instrument panels, door trims, seat fabrics, door handles, floor mats, etc. .

For household appliances and electronic applications, personal computer housings and internal parts, CRT display and LCD housings and internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile personal computers, handheld types, recording media (CDs) , DVD, MD, FDD, etc.) Useful for housings and internal parts of drives, housings and internal parts of copiers, facsimiles, and other electronic and home appliances such as VTRs, digital cameras, TVs, refrigerators, and air conditioners In the packaging field, various packaging is possible as a foaming buffer, a packaging film, and a sheet. In the medical field, it can be used as sanitary materials such as medical materials and sanitary products. In addition, it is also useful for leisure goods, cards such as IC cards, trays, plastic cans, containers and tableware such as containers, tanks, and baskets, bags, chairs, tables, and the like.
Furthermore, the aliphatic polyester resin composition of the present invention may include a conventionally known plasticizer, antioxidant, heat stabilizer, light stabilizer, ultraviolet absorber, hydrolysis inhibitor, antistatic agent, release agent, if necessary. Various additives such as molds, fragrances, lubricants, flame retardants, foaming agents, pigments, colorants, various fillers, fillers, reinforcing materials, antibacterial and antifungal agents may be blended.

EXAMPLES Next, although an Example and a reference example demonstrate this invention in detail, these do not limit this invention.
The characteristic evaluation of the resin composition molded article was as follows.
(1) Charpy impact strength (notched): Measured at 25 ° C. under the conditions of ISO179-1 / 1eA using 80 mm × 10 mm × 4 mm test pieces in accordance with ISO179 standard. In Table 1, (P) indicates Partial Break.
(2) Deflection temperature under load (HDT): In accordance with ISO75-1.2 standard, an 80 mm × 10 mm × 4 mm test piece was measured under the condition that the bending stress applied to the test piece was 0.45 MPa.

The characteristics of the aliphatic polyester resin were evaluated as follows.
(3) Molecular weight GPC [Tosoh HLC-8120GPC, detection RI, column is TSK gel GMHHR-M], the solvent was tetrahydrofuran, the measurement temperature was 40 ° C., and the weight average molecular weight was calculated in terms of commercially available standard polystyrene.
(4) Optical purity, L-form / D-form composition ratio Hydrolyzed with 1N-NaOH aqueous solution using HPLC [LC-10A-VP UV (254 nm) detection made by Shimadzu Corporation] equipped with optical isomer separation column, HCl Using the aqueous solution neutralized with the sample, the ratio of L-form and D-form was determined.

(5) Melting point and glass transition temperature Using DSC [Pyris 1 manufactured by Perkin Elmer], the melting point and glass transition temperature were determined by a temperature change of 20 ° C./min in a nitrogen atmosphere.
The properties of the block copolymer when the conjugated diene block copolymer was used as the elastomer were evaluated as follows.
(6) Styrene content It computed from the absorption intensity of 262 nm using the ultraviolet spectrophotometer (Hitachi UV200).
(7) The amount of 1,2 bonds and the hydrogenation rate were measured using a nuclear magnetic resonance apparatus (DPX-400 manufactured by BRUCKER).

(8) Weight average molecular weight GPC [Measured by LC10 manufactured by Shimadzu Corporation, column by Shimpac GPC805 + GPC804 + GPC804 + GPC803 manufactured by Shimadzu Corporation], tetrahydrofuran was used as a solvent, and measurement conditions were performed at a temperature of 35 ° C. The weight average molecular weight was obtained by using a calibration curve (created using the peak molecular weight of standard polystyrene) obtained by measuring the molecular weight of the peak of the chromatogram from measurement of commercially available standard polystyrene. The molecular weight when there are a plurality of peaks in the chromatogram refers to the average molecular weight determined from the molecular weight of each peak and the composition ratio of each peak (determined from the area ratio of each peak in the chromatogram).

(9) Number average molecular weight of styrene homopolymer block A method of oxidatively decomposing a block copolymer with di-tert-butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et-al., J. MoI. Polym.Sci. 1,429 (1946)), a styrene homopolymer block component was obtained from the block copolymer before hydrogenation (however, the component having a polymerization degree of 30 or less was removed), and GPC measurement of the component was performed. Determined by

(10) Content of styrene homopolymer block (block rate)
The styrene homopolymer block obtained by the above oxidative decomposition was analyzed with an ultraviolet spectrophotometer and calculated using the following formula.
Block ratio (%) = (% by weight of styrene homopolymer block in hydrogenated block copolymer) / (% by weight of total styrene in hydrogenated block copolymer) × 100
Aliphatic polyester resins used in the following examples are known, for example, “Polylactide” in Biopolymers Vol. 4 (Wiley-VCH 2002) PP129-178 and polylactic acid (A-1) produced by a ring-opening polymerization method of lactide using a tin-based catalyst according to JP-T-050547331.
The weight average molecular weight, D-form content, glass transition temperature, and melting point of (A-1) were 189,000, 1.1%, 58 ° C, and 170 ° C, respectively.
Furthermore, the manufacture example of the modified conjugated diene type polymer used in the following examples is shown.

[Production Example 1] Modified conjugated diene polymer; B-1
The autoclave with a stirrer and jacket is washed, dried, purged with nitrogen, charged with a cyclohexane solution containing 85 parts by weight of pre-purified butadiene (concentration 15% by weight), and then tetrahydrofuran is used for the n-butyllithium used. After adding 1.5 moles per mole, the reactor internal temperature was maintained at 50 ° C. As a polymerization initiator, 0.1 part by weight of n-butyllithium was added with respect to 100 parts by weight of all monomers used. After the start of the reaction, the internal temperature of the reactor gradually increased due to heat generated by polymerization. After completion of the reaction, a cyclohexane solution containing 15 parts by weight of pre-purified styrene (concentration 15% by weight) was added to continue the polymerization, and the final reactor internal temperature reached about 70 ° C.
Next, an equimolar amount of 1,3-dimethyl-2-imidazolidinone (hereinafter referred to as modifier M1) as a modifier is added to the living polymer obtained in the above with respect to n-butyllithium used for polymerization. To complete the reaction. Methanol was then added, and then 0.3 parts by weight of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the polymer.
The resulting modified conjugated diene copolymer (B-1) had a styrene content of 15% by weight, a block styrene content of 14% by weight, a vinyl bond content of 14%, and a weight average molecular weight of 12.9 million. It was.

[Production Example 2] Modified conjugated diene polymer; B-2
In the same manner as in Production Example 1, a modified block copolymer obtained by modification with a modifier M1 was charged with 2 liters of dried and purified cyclohexane in a reaction vessel purged with nitrogen, and bis (η5-cyclopentadienyl) titanium. Add 100 mmol of dichloride, add n-hexane solution containing 200 mmol of trimethylammonium with thorough stirring, and add 100 ppm of Ti per polymer as a hydrogenation catalyst obtained by reacting at room temperature for about 3 days. The hydrogenation reaction was performed for 1 hour at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. However, the amount of hydrogen used for hydrogenation was adjusted so that the hydrogenation rate of the resulting hydrogenated product was 22%. Thereafter, methanol was added, and then octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was 0.3 parts by mass with respect to 100 parts by weight of the block copolymer. The modified conjugated diene copolymer (B-2) which was added and partially hydrogenated was obtained.

[Production Example 3] Modified conjugated diene polymer; B-3
The autoclave with a stirrer and jacket was washed, dried, purged with nitrogen, and a cyclohexane solution (concentration 20% by weight) containing 15 parts by weight of styrene purified in advance was added. Next, 0.1 mol of n-butyllithium is added to 1 mol of n-butyllithium using tetramethylethylenediamine, and then 0.135 parts by weight of n-butyllithium is added to 100 parts by weight of all the monomers used, and then at 70 ° C. for 1 hour. After polymerization, a cyclohexane solution containing 70 parts by weight of pre-purified butadiene (concentration 20% by weight) was added and polymerized at 70 ° C. for 1 hour, and then further cyclohexane solution containing 15 parts by weight of pre-purified styrene (concentration 20% by weight). ) And polymerized at 70 ° C. for 1 hour.
Next, the living polymer obtained above was added in an equimolar amount to the n-butyllithium used in the polymerization for the modifier M1 to complete the reaction. Methanol was then added, and then 0.3 parts by weight of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the polymer.
The resulting modified conjugated diene copolymer (B-3) had a styrene content of 30% by weight, a block styrene content of 29% by weight, a vinyl bond content of 15%, and a weight average molecular weight of 11 million. It was.

[Production Example 4] Unmodified conjugated diene polymer; B-4
Polymerization was carried out in the same manner as in Production Example 1, but no modifier was added, methanol was added directly, and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer. 0.3 part by weight was added to 100 parts by weight of the polymer.

[Production Example 5] Unmodified conjugated diene polymer; B-5
The autoclave with a stirrer and jacket was washed, dried, purged with nitrogen, and charged with a cyclohexane solution (concentration 20% by weight) containing 10 parts by weight of styrene purified in advance. Next, 0.3 mol per 1 mol of n-butyllithium using tetramethylethylenediamine was added, and then 0.9 parts by weight of n-butyllithium was added with respect to 100 parts by weight of all monomers used, and one hour at 70 ° C. After polymerization, a cyclohexane solution containing 80 parts by weight of pre-purified butadiene (concentration of 20% by weight) was added and polymerized at 70 ° C. for 1 hour, and then further cyclohexane solution containing 10 parts by weight of pre-purified styrene (concentration of 20% by weight). ) And polymerized at 70 ° C. for 1 hour. Methanol was then added, and then 0.3 parts by weight of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the polymer.
The resulting unmodified conjugated diene copolymer (B-5) had a styrene content of 20% by weight, a block styrene content of 19% by weight, a vinyl bond content of 33%, and a weight average molecular weight of 125,000. there were.

[Example 1]
10 parts by weight of elastomer B-1 and 5 parts by weight of talc (manufactured by Nippon Talc Co., Ltd., fine talc, P-3) are dry blended with 90 parts by weight of aliphatic polyester resin A-1, and then the same direction biaxial extrusion Using a machine (Ikegai Iron Works Co., Ltd., PCM-30), the mixture was melt kneaded at a cylinder temperature of 190 ° C., cooled, and then cut to obtain a pellet-like aliphatic polyester resin composition. The obtained resin composition was injection molded at a mold temperature of 30 ° C. and a cooling time of 30 seconds to obtain a test piece. The test piece was heat-treated at 120 ° C. for 30 minutes, and then physical properties were evaluated.

[Example 2]
A test piece was obtained and evaluated in the same manner as in Example 1 except that 95 parts by weight of aliphatic polyester resin A-1 and 5 parts by weight of elastomer B-1 were used.

[Example 3]
A test piece was obtained and evaluated in the same manner as in Example 1 except that 80 parts by weight of aliphatic polyester resin A-1 and 20 parts by weight of elastomer B-1 were used.

[Example 4]
After dry blending 90 parts by weight of aliphatic polyester resin A-1 and 10 parts by weight of elastomer B-2, the cylinder temperature was 190 ° C. in the same direction twin screw extruder (Ikegai Iron Works Co., Ltd., PCM-30). Then, the strand was cooled and then cut to obtain a pellet-shaped aliphatic polyester resin composition. The obtained resin composition was injection molded at a mold temperature of 30 ° C. and a cooling time of 30 seconds to obtain a test piece. The test piece was heat-treated at 120 ° C. for 30 minutes, and then physical properties were evaluated.

[Example 5]
A test piece was obtained and evaluated in the same manner as in Example 4 except that the type of elastomer was changed to B-3.
The evaluation results of Examples 1 to 5 are shown in Table 1.
In addition, although the impact test value describes the maximum value, the sample did not reach the fracture state, and this state was described as NB.

[Comparative Example 1]
Aliphatic polyester resin A-1 was injection-molded at a mold temperature of 30 ° C. and a cooling time of 30 ° C., and taken out of the mold, and then heat-treated at 120 ° C. for 30 minutes to obtain a test piece, which was evaluated for physical properties.

[Comparative Example 2]
In the same manner as in Example 1, 10 parts by weight of elastomer B-1 and 5 parts by weight of talc (manufactured by Nippon Talc Co., Ltd., fine powder talc, P-3) were melt-mixed with 90 parts by weight of aliphatic polyester resin A-1. The mixture was kneaded to obtain a pellet-shaped aliphatic polyester resin composition. The obtained resin composition was injection molded at a mold temperature of 30 ° C. and a cooling time of 30 seconds to prepare a test piece, and the physical properties were evaluated as it was.

[Comparative Example 3]
A resin composition was obtained in the same manner as in Example 5, and a test piece was prepared by injection molding at a mold temperature of 30 ° C. and a cooling time of 30 seconds.

[Comparative Example 4]
A test piece was obtained and evaluated for physical properties in the same manner as in Example 4 except that 10 parts by weight of B-4 was used as the elastomer.

[Comparative Example 5]
A test piece was obtained and evaluated for physical properties in the same manner as in Example 4 except that 10 parts by weight of B-5 was used as the elastomer.
The evaluation results of Comparative Examples 1 to 5 are shown in Table 2.
The aliphatic polyester resin molded product of the present invention was a molded product having a good molded appearance and excellent impact resistance and heat resistance.

  The aliphatic polyester resin molded article of the present invention is a molded article that is biodegradable and has both excellent impact resistance and heat resistance. This molded body can be molded into various shapes by various methods, and is a film, sheet, injection molded body, blow molded body, extruded molded body, vacuum / pressure molded body, laminated structure, container, foam, fiber, textile As a non-woven fabric, it can be used in various fields such as automobile field, electric / electronic field, packaging field, agricultural field, fishery field, medical field, and other general goods.

Claims (7)

It consists of a resin composition mainly composed of an aliphatic polyester resin, and has a Charpy impact strength at 25 ° C. of 15 to 230 kJ / m ² and a heat deformation temperature of 100 to 170 ° C. under a load of 0.45 MPa. Aliphatic polyester resin molding.   The aliphatic polyester resin molded article according to claim 1, wherein the aliphatic polyester resin composition comprises an aliphatic polyester resin (A) and an elastomer (B).   The aliphatic polyester resin composition according to claim 1 or 2, wherein the component (B) is a modified conjugated diene copolymer.   (B) Modified conjugated diene polymer wherein the component is modified with a compound having at least one polar group selected from an amino group, an imino group, a hydroxyl group, an epoxy group, a carboxyl group and an acid anhydride group The aliphatic polyester resin composition according to any one of claims 1 to 3.   (B) A modified conjugate in which the component is a compound having at least one polar group selected from an amino group, an imino group, a hydroxyl group, an epoxy group, a carboxyl group, and an acid anhydride group, the terminal of which is modified It is a diene polymer, The aliphatic polyester resin composition in any one of Claims 1-4 characterized by the above-mentioned.   The aliphatic polyester resin molded article according to any one of claims 1 to 5, wherein the component (B) is a modified conjugated diene copolymer modified with a compound having an imidazolidinone skeleton.   The aliphatic polyester resin composition according to any one of claims 1 to 6, wherein the aliphatic polyester resin composition contains (C) a crystal nucleating agent.