JP2006008743A - Molding of aliphatic polyester-based resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a molding of an aliphatic polyester-based resin composition having excellent impact resistance. <P>SOLUTION: The molding is a molding of an aliphatic polyester resin composition composed of an aliphatic polyester (a) and an elastic polymer (b). The relation between Tan&delta; at 80&deg;C and Tan&delta; at 65&deg;C satisfies the formula; Tan&delta;(80)/Tan&delta;(65)&gt;1.00 (Tan&delta;(80) is Tan&delta; of molding at 80&deg;C;Tan&delta;(65) is Tan&delta; of molding at 65&deg;C). <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a molded article of an aliphatic polyester resin composition excellent in impact resistance.

Recently, due to the increasing awareness of environmental problems, biodegradable polymers that are degraded in the natural environment by the action of microorganisms that exist in nature have attracted attention, and various biodegradable polymers have been developed. Among these, as a biodegradable polymer that can be melt-molded, for example, polyethylene comprising an aliphatic dicarboxylic acid component such as polyhydroxybutyrate, polycaprolactone, succinic acid or adipic acid and a glycol component such as ethylene glycol or butanediol. Aliphatic polyesters such as succinate, polybutylene adipate and polylactic acid are known.
Among them, polylactic acid has been extensively studied for practical use. However, aliphatic polyesters including polylactic acid generally have brittleness and low impact resistance, and have problems that it is difficult to express impact resistance when molded by a practical molding method because of slow crystallization. Was. For the spread of biodegradable polymers, especially the expansion of use as molded products, improvement of impact resistance has become an important issue.

Conventionally, many blends of polycaprolactone having a low glass transition temperature and an aliphatic polyester derived from glycol and an aliphatic dibasic acid have been studied for the development of impact resistance of polylactic acid. These blends are intended to maintain biodegradability, which is one of the characteristics of polylactic acid, and to impart flexibility, but the impact resistance is not sufficiently improved.
In general, it is known to blend a conjugated diene polymer in order to improve impact resistance of a thermoplastic resin or the like. As a blend of such a conjugated diene copolymer with polylactic acid, for example, a resin composition of polylactic acid and an epoxidized diene block copolymer is known (for example, see Patent Document 1). However, in these techniques, in order to increase impact resistance, it is necessary to blend a large amount of soft components with the polylactic acid-based resin. Therefore, development of a technique for imparting more effective impact resistance is required. Also disclosed is a system in which polylactic acid is mixed with ethylene-propylene-diene rubber (EPDM) (for example, see Patent Document 2). In this system, EPDM is simply mixed with polylactic acid or a crosslinking reaction is performed with a radical reaction initiator, but the impact resistance is not improved sufficiently.
JP 2000-219803 A JP 2002-37987 A

  An object of this invention is to provide the new molded object to which the impact resistance was provided to aliphatic polyester-type resin.

  In order to solve the above problems, the inventors of the present invention have studied a molded product composed of an aliphatic polyester and an elastic polymer, and the molecular chain containing the elastic polymer and forming the amorphous portion of the aliphatic polyester. It has been found that impact resistance is exhibited when the movement is restrained, and the present invention has been completed. As is generally known, for example, a hard resin such as polylactic acid is dispersed in a soft component such as an elastic polymer by using it as a matrix. The impact strength is expressed by the generated shear yield or craze. Further, when the stress at which craze is formed is higher than the shear yield stress, the shear yield occurs preferentially and the impact strength is more easily expressed. When the sufficient craze formation stress cannot be obtained only by the entanglement of the molecular chain, the inventors have made the crystal lamella a physical cross-linking point when the molecular chain is sufficiently crystallized, and the craze formation stress is further improved and the impact strength is improved. In addition, the presence of a large number of tie molecules that connect the crystal lamellae effectively considered the function of the crystal lamella as a physical crosslinking point and improved the impact strength. The amount of crystal lamellae can be determined by crystal melting calorimetry in differential scanning calorimetry (DSC), wide-angle X-ray analysis, etc. The number of tie molecules is determined by dynamic viscoelasticity, and the mobility of amorphous molecular chains. It can be determined by measuring. That is, it can be determined that the number of tie molecules is large when the Tanδ peak has a high temperature side component by the measurement of Tanδ. The inventors of the present invention have clarified that the impact resistance of the molded article is improved when the number of tie molecules, that is, the high temperature side component of the Tan δ peak is large, and completed the present invention.

That is, the present invention
1. A molded product of a composition comprising an aliphatic polyester (a) and an elastic polymer (b), wherein the relationship between Tan δ at 80 ° C. and Tan δ at 65 ° C. satisfies the following formula:
Tan δ (80) / Tan δ (65)> 1.00
Tan δ (80): Tan δ of the molded body at 80 ° C.
Tan δ (65): Tan δ of the molded body at 65 ° C.
2. An elastic polymer in which component (b) 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 molded product according to 1 above, which is characterized by
3. Component (b) 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, and the terminal thereof is modified. The molded article according to any one of the above items 1 and 2, which is an elastic polymer,
4. The molded product according to any one of 1 to 3, wherein the polar group is an amino group and / or an imino group,
5. The molded product according to any one of 1 to 4 above, wherein the component (b) is a modified polymer modified with a modifying agent having an imidazolidinone skeleton.
6. Component (b) is a modifier in which an atomic group having a functional group is bonded to the living terminal of a conjugated diene polymer obtained by polymerizing an organolithium compound as a polymerization initiator, or an atomic group in which the functional group is protected. It is an elastic polymer obtained by reacting a modifying agent to which is bonded, or an elastic polymer modified by reacting with the first functional group with a secondary modifying agent having another functional group. The molded product according to any one of 1 to 5,
7. The molded product according to any one of 1 to 6 above, wherein the component (b) is a homopolymer of a conjugated diene and / or an elastic polymer in which a copolymer of a conjugated diene and a vinyl aromatic compound is modified. ,
8. The component (b) is an elastic polymer in which a copolymer comprising at least one block mainly composed of a vinyl aromatic compound and at least one block mainly composed of a conjugated diene is modified. The molded product according to any one of 1 to 7 above,
9. The molded product according to any one of 1 to 8 above, wherein the component (b) is an elastic polymer in which a hydrogenated polymer is modified.
10. The molding according to any one of 1 to 9 above, wherein the composition is a composition comprising (a) 60 to 99.9 parts by weight and (b) 0.1 to 40 parts by weight of the component. body,
11. The molded article according to any one of 1 to 10 above, wherein the composition further comprises a crystal nucleating agent (c) component,
12. The molded product according to 11 above, wherein the composition contains 1 to 50 parts by weight of component (c) with respect to 100 parts by weight of both component (a) and component (b).
13. The molded product according to any one of 1 to 12, wherein the molded product is injection-molded,
14, the molded product according to any one of 1 to 13, wherein the component (a) is a polylactic acid resin,
It is.

  By this invention, the aliphatic polyester resin composition molded object excellent in impact resistance is obtained, and the utilization range of the aliphatic polyester-type resin to various molded articles is expanded.

Hereinafter, the present invention will be specifically described.
The aliphatic polyester (a) 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 (1) is a polymer containing L-lactic acid and / or D-lactic acid as a main constituent component, but other copolymer components other than lactic acid are used as long as the object of the present invention is not impaired. .1 to 99.9% by weight may be contained. Examples of such other copolymer component units include polyvalent carboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones, and the like. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , Azelaic acid, sebacic acid, dodecanedioic acid, fumaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium sulfoisophthalic acid Polyhydric carboxylic acids such as ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, trimethyl Propanediol, pentaerythritol, bisphenol A, aromatic polyhydric alcohols obtained by addition reaction of ethylene oxide with bisphenol, polyhydric alcohols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycolic acid, Hydroxycarboxylic acids such as 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid, hydroxybenzoic acid, glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ- Lactones such as butyrolactone, β- or γ-butyrolactone, pivalolactone, and δ-valerolactone can be used. These copolymer components can be used alone or in combination of two or more.

  As a method for producing a polylactic acid resin, a known polymerization method can be used. In particular, for polylactic acid, a direct polymerization method from lactic acid, a ring-opening polymerization method via lactide, or the like can be employed. The polylactic acid resin in the present invention is a polymer mainly composed of lactic acid, that is, L-lactic acid or D-lactic acid. In the polylactic acid-based resin, the constituent molar ratio of the L-lactic acid unit to the D-lactic acid unit is preferably 85% or more for either the L-form or D-form relative to 100% of the L-form and D-form. One is preferably 90% or more, and more preferably one is 94% or more. When the crystallinity is increased and heat resistance is required, it is preferable to increase the optical purity, and one is preferably 98% or more. In addition, a stereocomplex formed from poly-L lactic acid mainly composed of L-lactic acid units and poly-D lactic acid mainly composed of D-lactic acid units can also be preferably used in order to enhance crystallinity.

The polylactic acid-based resin may be copolymerized with other components copolymerizable with lactic acid monomer or lactide other than L-form or D-form, such as dicarboxylic acid, polyhydric alcohol, hydroxycarboxylic acid, Examples include lactones. The polylactic acid resin can be polymerized by a known polymerization method such as direct dehydration condensation or ring-opening polymerization of lactide. If necessary, the molecular weight can be increased by using a binder such as polyisocyanate.
The preferred weight average molecular weight range of the polylactic acid resin (1) is 30,000 to 1,000,000, more preferably 50,000 to 500,000, and most preferably 100,000 to 280,000. The weight average molecular weight is preferably 30,000 or more in consideration of the mechanical properties of the composition, and is preferably 1,000,000 or less in consideration of processability due to an increase in melt viscosity.

  The aliphatic polyester (a) in the aliphatic polyester resin composition of the present invention is preferably 99.9 to 60% by weight, more preferably 99.8 to 70% by weight, still more preferably 99 to 80% by weight, particularly preferably. Is preferably 98 to 85% by weight, and the elastic polymer (b) is preferably 0.1 to 40% by weight, more preferably 0.2 to 30% by weight, still more preferably 1 to 20% by weight, and particularly preferably 2 to 15% by weight. (A) is preferably 99.9% by weight or less, more preferably 99.8% by weight or less in consideration of improvement in impact resistance, and 60% by weight in consideration of elastic modulus and heat resistance from the viewpoint of use as a molded product. The above is preferable, and 70% by weight or more is more preferable.

One example of the elastic polymer (b) used in the present invention is an olefin polymer, and examples thereof include ethylene homopolymers such as LDPE and LLDPE, and ethylene / α-olefin copolymers. -A polyolefin-based elastomer comprising an α-olefin copolymer is preferred.
The ethylene / α-olefin copolymer is a copolymer composed of ethylene and an α-olefin having 3 to 20 carbon atoms such as propylene, 1-butene, 1-hexene, 1-octene and the like. These α-olefins may be used alone or in combination of two or more. Further, non-conjugated dienes such as conjugated dienes such as 1,3-butadiene and isoprene, dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and ethylidene norbornene may be copolymerized.

  These olefin polymers are olefin polymers 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. It is preferable in terms of impact resistance. Particularly preferred polar groups are amino groups and imino groups. By combining atomic groups having such a polarity, the effect of improving the impact resistance of the polylactic acid resin becomes remarkable. As a method of modifying these olefin polymers 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, a polar group is used. A known method such as a method of adding a compound having a unsaturated group having a compound to a polymer chain using a radical initiator or the like, or a copolymerization of a monomer having a polar group with ethylene or the like can be used.

  The conjugated diene polymer which is another example of the elastic polymer (b) is a homopolymer of a conjugated diene, a copolymer of a conjugated diene and a vinyl aromatic compound, 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.

  As the vinyl aromatic compound, one of styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, etc. Alternatively, two or more types can be used, and styrene is generally preferable. The content of the vinyl aromatic compound in the copolymer is 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less, and most preferably 25% by weight or less. Considering the effect of imparting impact resistance, it is preferably 50% by weight or less. Both units may be randomly copolymerized, copolymerized in a block form, or a copolymer containing a block copolymerized by random copolymerization, but preferably at least one mainly composed of a vinyl aromatic compound, for example. A block copolymer comprising at least one polymer block A and at least one polymer block B mainly comprising a conjugated diene, or a hydrogenated product thereof. More preferably, it is a block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and one polymer block B mainly composed of a conjugated diene.

Examples of the method for producing the vinyl aromatic compound elastomer (2) used in the present invention include Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-171979, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957. Gazette, JP-B 48-2423, JP-B 48-4106, JP-B 56-28925, JP-B 51-49567, JP-A 59-166518, JP-A 60-186777 The method described in the gazette gazette etc. is mentioned. 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] mX, [(AB) n] mX,
[(BA) n-B] m-X, [(AB) n-A] m-X
(In the above formula, A is a polymer block mainly composed of a vinyl aromatic compound, B is a polymer block mainly composed of a conjugated diene, and X is a residue of a coupling agent or a polyfunctional organolithium compound) In addition, 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 a vinyl aromatic hydrocarbon is preferably a vinyl aromatic compound containing 50% by weight or more, more preferably 70% by weight or more of a vinyl aromatic compound and a conjugated diene. A copolymer block or / and a vinyl aromatic compound homopolymer block are shown, 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 compound or / and a conjugated diene homopolymer block containing at least% by weight is shown. The vinyl aromatic compound 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 compound is uniformly distributed and / or a portion where the vinyl aromatic compound is distributed in a tapered shape may coexist.

  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.

In the hydrogenated 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, and is not particularly limited. 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. In addition, there is no restriction | limiting in particular about the hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in a copolymer.
The weight average molecular weight of the conjugated diene polymer used in the present invention is preferably 30,000 or more from the viewpoint of the impact resistance improvement effect of the composition, and preferably 1,000,000 or less from the viewpoint of workability, more preferably 60,000 to 800,000, More preferably, it is 70,000 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 compound homopolymer block is determined by oxidative decomposition with ditertiary 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 the modified block copolymer before hydrogenation (however, the degree of polymerization is 30 or less). The amount of the component is removed using an ultraviolet spectrophotometer or the like.
The conjugated diene polymer used in the present invention is a conjugate 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. It is a diene polymer (hereinafter referred to as a modified conjugated diene polymer).

Among these, the polymer terminal is modified with a compound having 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. The characteristic conjugated diene polymer is preferred from the viewpoint of impact resistance.
In the present invention, the polymer terminal is modified with a compound having at least one polar group or at least one group selected from an amino group, an imino group, a hydroxyl group, an epoxy group, a carboxyl group, and an acid anhydride group. Diene homopolymers, copolymers of conjugated dienes and vinyl aromatic compounds, or hydrogenated products thereof can be preferably used, and may be used in combination.
Particularly preferred polar groups are amino groups and imino groups. In the present invention, the amino group means each polar group characterizing not only a primary amine but also a secondary amine and a tertiary amine.

In the present invention, the imino group means a group in which a nitrogen atom is bonded to the same carbon atom with a double bond, that is, = NH.
By combining atomic groups having such a polarity, the effect of improving the impact resistance of the polylactic acid resin becomes remarkable.
The modified conjugated diene polymer can be produced by adding a compound having a polar group using a radical initiator in the same manner as the olefin polymer, or sealing the anionic polymerization active terminal with a compound having a polar group. It can be obtained using a known method such as stopping. These can be produced according to, for example, the descriptions in JP-A-8-3250, JP-A-10-189255, JP-2002-201333, JP-A-2002-317024, JP-A-2003-113202, and the cited references. is there.

For the method of sealing with a compound having a polar group, there is a modifier in which an atomic 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. The method of making the modifier | denaturant which has couple | bonded react is mentioned. 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 modified conjugated diene polymer, it is preferable that at least one compound having a polar group is bonded to one polymer chain. Examples thereof include a modified conjugated diene polymer in which a compound having a polar group is bonded to the terminal in one polymer chain. The modified conjugated diene polymer may contain an unmodified conjugated diene polymer.

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 which 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.
Elastic weight characterized by being 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 used in the present invention. The amount of the polar group in the union (b) is preferably 0.00001% by weight or more and 30% by weight or less, more preferably 0.00001% by weight or more and less than 5% by weight, and 0.00001% by weight or more. It is particularly preferred that it is 1% by weight or less.

  In the present invention, an amino group, an imino group, a hydroxyl group, an epoxy group and a conjugated diene copolymer modified with a carboxyl group and an acid anhydride group described later can be used to obtain a hydroxyl group, an epoxy group, an amino group. Examples of the atomic group having at least one functional group selected from a group, a silanol group, and an alkoxysilane include an atomic group 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 R ^{12 to} R ¹⁴ and R ¹⁰ hydrocarbon chain are bonded with elements such as oxygen, nitrogen, silicon and the like in a bonding mode other than hydroxyl, epoxy, silanol, and alkoxysilane. R ¹¹ is hydrogen or an alkyl group having 1 to 8 carbon atoms.)
In the present invention, an amino group, an imino group, a hydroxyl group, an epoxy group, and a hydroxyl group, an epoxy group, which can be used to obtain a conjugated diene copolymer modified with a carboxyl group and an acid anhydride group described later, Examples of the modifier used to obtain a conjugated diene polymer in which at least one atomic group having at least one functional group selected from an amino group, a silanol group, and an alkoxysilane is bonded include the following. It is done.

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.

Further, 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) ethyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

  Β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, β- ( 3,4-epoxycyclohexyl) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethylethyldimethoxysilane, β- (3,4-epoxy Cyclohexyl) ethylethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldipropoxysilane, β- (3,4-epoxycyclohexyl) Ethyl methyl dibutoxy Emissions, and the like.

  Β- (3,4-epoxycyclohexyl) ethylmethyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyldimethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyldiethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyldimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyldimethylpropoxysilane, β- (3,4-epoxycyclohexyl) ethyldimethylbutoxysilane, β- (3,4 Epoxycyclohexyl) ethyldimethylphenoxysilane, β- (3,4-epoxycyclohexyl) ethyldiethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiisopropeneoxysilane, 1,3-dimethyl-2-imidazo Lydinon 1,3-diethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea, N-methylpyrrolidone, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine Among them, a modifier having an imidazolidinone skeleton such as 1,3-dimethyl-2-imidazolidinone and 1,3-diethyl-2-imidazolidinone is particularly 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, the method for obtaining a conjugated diene polymer modified with a carboxyl group or an acid anhydride group is a method in which a polar group selected from the aforementioned hydroxyl group, amino group, imino group, epoxy group, silanol group, and alkoxysilane is used. Examples thereof include a method in which a conjugated diene polymer having at least one atomic group having at least one atomic group is reacted 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 anhydride.

  In addition, as another method for obtaining a 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 or ester thereof. And a method of graft-modifying with an amide, an amid, and an imidate. Specific examples of the α, β-unsaturated carboxylic acid or derivative 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 conjugated diene polymer.

In the molded body of the present invention, the relationship between Tan δ at 80 ° C. and Tan δ at 65 ° C. must satisfy the following equation.
Tan δ (80) / Tan δ (65)> 1.00
Tan δ (80): Tan δ of the molded body at 80 ° C.
Tan δ (65): Tan δ of the molded body at 65 ° C.
When the value of Tan δ (80) / Tan δ (65) is 1.00 or more, the number of tie molecules is sufficient, so that sufficient impact resistance can be obtained. The preferred range is Tanδ (80) / Tanδ (65) value of 1.70 or more, more preferred range is 1.80 or more, and particularly preferred range is 2.00 or more. The value of Tan δ can be measured using a dynamic viscoelasticity measuring apparatus. In order to set the value of Tan δ (80) / Tan δ (65) within the range of the present invention, it is important to solidify at a high speed during molding. Many tie molecules are difficult to form unless solidified at high speed. In order to solidify at a high speed, for example, techniques such as improving the optical purity of the polylactic acid resin, introducing a crystal nucleating agent, or introducing a polylactic acid stereocomplex can be used. It is also possible to set the mold temperature relatively low and increase the solidification rate, but in this case, sufficient crystallinity is achieved by techniques such as post-crystallization, which increases the holding time in the mold. It is important in terms of impact resistance. In the present invention, in the crystalline melting curve of the aliphatic polyester (a) in the molded product, the value of the melting enthalpy ΔH is desirably more than 20 J / g from the viewpoint of impact resistance, and a preferable range is ΔH ≧ 25 J / g. A more preferable range is ΔH ≧ 30 J / g. The ΔH value of the molded body can be determined by differential scanning calorimetry (DSC).

  In the present invention, by adding the crystal nucleating agent (c), it is possible to further enhance the impact resistance imparting effect of the component (b). The shape of the crystal nucleating agent (c) is not particularly limited, and any particle shape, plate shape, or whisker shape can be used. As preferred crystal nucleating agents, those generally used as polymer crystal nucleating agents can be used without particular limitation, and both inorganic crystal nucleating agents and organic crystal nucleating agents can be used. From the viewpoint of impact resistance, it is preferable to contain 1 to 50 parts by weight of component (c) with respect to 100 parts by weight of both component (a) and component (b). When the amount is 1 part by weight or more, crystallization occurs, which is preferable because the impact resistance is improved.

  Specific examples of inorganic crystal nucleating agents include talc, kaolinite, montmorillonite, synthetic mica, clay, zeolite, silica, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, Examples thereof include metal salts of barium sulfate, aluminum oxide, neodymium oxide and phenylphosphonate. These inorganic crystal nucleating agents are preferably modified with an organic substance in order to enhance dispersibility in the composition.

  Specific examples of organic crystal nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, Calcium oxide, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicylic acid , Metal salts of organic carboxylic acids such as aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearic acid Carboxylic acid amides such as amide, ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, and trimesic acid tris (t-butylamide) can be mentioned.

  In addition, polymers such as low density polyethylene, high density polyethylene, polypropylene, polyisopropylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, high melting point polylactic acid, Sodium salt or potassium salt of a polymer having a carboxyl group such as sodium salt of ethylene-acrylic acid or methacrylic acid copolymer, sodium salt of styrene-maleic anhydride copolymer (so-called ionomer), benzylidene sorbitol and its derivatives, sodium 2,2 Examples include phosphorus compound metal salts such as' -methylenebis (4,6-di-t-butylphenyl) phosphate, and 2,2-methylbis (4,6-di-t-butylphenyl) sodium. It can be.

As the crystal nucleating agent used in the present invention, among those exemplified above, at least one selected from talc, kaolin, calcium carbonate, and organic carboxylic acid metal salt is particularly preferable. The crystal nucleating agent used in the present invention may be used alone or in combination of two or more.
As the plasticizer used in the present invention, those generally known can be used. For example, polyester plasticizer, glycerin plasticizer, polyvalent carboxylic acid ester plasticizer, phosphate ester plasticizer. And polyalkylene glycol plasticizers and epoxy plasticizers. Specific examples of the polyester plasticizer include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, propylene glycol, 1,3-butanediol, 1,4-butane. Examples thereof include polyesters composed of diol components such as diol, 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acid such as polycaprolactone.

  These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol, or may be end-capped with an epoxy compound or the like. Specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomonomontanate. Specific examples of polycarboxylic acid ester plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, and butyl benzyl phthalate. Citric acid esters such as tributyl acid, trioctyl trimellitic acid, trihexyl trimellitic acid, trimellitic acid ester such as trihexyl trimellitic acid, diisodecyl adipate, n-octyl-n-decyl adipate, triethyl acetylcitrate, tributyl acetylcitrate Examples include acid esters, azelaic acid esters such as di-2-ethylhexyl azelate, sebacic acid esters such as dibutyl sebacate, and di-2-ethylhexyl sebacate.

  Specific examples of the phosphate ester plasticizer include tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate and tricresyl phosphate. . Specific examples of the polyalkylene glycol plasticizer include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, bisphenols Polyalkylene glycols such as propylene oxide addition polymers, tetrahydrofuran addition polymers of bisphenols, or terminal-capped compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds.

  The epoxy plasticizer generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil, but there are also so-called epoxy resins mainly made of bisphenol A and epichlorohydrin. Can be used. Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, oleic acid Examples thereof include aliphatic carboxylic acid esters such as butyl, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils, and paraffins.

  Among the plasticizers used in the present invention, at least one selected from polyester plasticizers and polyalkylene glycol plasticizers is preferable among those exemplified above. Only one type of plasticizer may be used in the present invention, or two or more types may be used in combination. Moreover, the compounding quantity of a plasticizer has the preferable range of 0.01-30 weight part with respect to a total of 100 weight part of (a) component and (b) component, and the range of 0.1-20 weight part is more. The range of 0.5 to 10 parts by weight is more preferable.

  For the resin composition of the present invention, a reinforcing material (glass fiber, carbon fiber, metal fiber, natural fiber, organic fiber, glass flake, glass bead, ceramic fiber, ceramic bead, asbestos, as long as the object of the present invention is not impaired. , Wollastonite, talc, clay, mica (natural, synthetic), sericite, zeolite, bentonite, montmorillonite, dolomite, kaolin, finely divided silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, sulfuric acid Barium, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dosonite or clay, stabilizers (hindered phenol, hydroquinone, phosphites and their substitutes, resorcinol, salicin Rate, benzotriazole, benzophenone, etc.), lubricant, mold release agent (montanic acid and its salts, its ester, its half ester, stearyl alcohol, stearamide and polyethylene wax), dye (such as nigrosine) and pigment (cadmium sulfide, phthalocyanine) Etc.), anti-coloring agents (phosphites, hypophosphites, etc.), flame retardants (red phosphorus, phosphate esters, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, magnesium hydroxide, 1 type or 2 or more types, such as a melamine and cyanuric acid or its salt), a electrically conductive agent or a coloring agent (carbon black etc.), a slidability improving agent (graphite, a fluororesin etc.), an antistatic agent, etc. it can.

  Moreover, in the composition in this invention, polymers other than (a) component and (b) component can be mixed in the range which does not impair the objective of this invention. Polymers other than component (a) and component (b) include polyolefins such as polyethylene and polypropylene, polyamides, acrylic resins, polyphenylene sulfide resins, polyether ether ketone resins, polyesters, polysulfones, polyphenylene oxides, polyimides, polyetherimides. Further, at least one or more of thermoplastic resins such as polyacetal and thermosetting resins such as phenol resin, melamine resin, silicone resin, and epoxy resin can be further added.

  Furthermore, arbitrary additives can be mix | blended according to various objectives within the range which does not impair the effect of this invention remarkably. The type of additive is not particularly limited as long as it is generally used for blending thermoplastic resins and elastic polymers. Inorganic fillers, pigments such as iron oxide, stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearamide, lubricants, mold release agents, paraffinic process oil, naphthenic process oil, Softeners and plasticizers such as aromatic process oil, paraffin, organic polysiloxane, mineral oil, hindered phenol antioxidants, antioxidants such as phosphorus heat stabilizers, hindered amine light stabilizers, benzotriazoles Examples include ultraviolet absorbers, flame retardants, antistatic agents, reinforcing agents such as organic fibers, glass fibers, carbon fibers, and metal whiskers, coloring agents, other additives, and mixtures thereof.

The production method of the composition in the present invention is not particularly limited, and a known method can be used. For example, it can be produced using a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a Brabender, or various kneaders. The composition comprising the aliphatic polyester (a) and the elastic polymer (b) includes a mixture that does not undergo melting of the components (a) and (b). In the present invention, a melt mixing method using an extruder is preferred from the viewpoint of productivity. When the crystal nucleating agent (c) is used, the components (a), (b), and (c) may be melt-kneaded all together, for example, the components (b) and (c) are pre-kneaded. Then, a divided kneading method in which the component (a) is melt kneaded is also possible. Also in the case of divided kneading, it is preferable to knead continuously from the viewpoint of productivity, such as kneading the components (b) and (c) first and then side feeding (a). In order to improve the dispersibility of the component (c), it is possible to adopt a mixing method in a solvent, and after sufficiently kneading with a heating roll or the like, the component (a) may be kneaded with an extruder. Is possible. Moreover, after pre-kneading a part of component (a) and component (b), it is also possible to add a component (a) and a component (c) as needed, and to obtain a desired composition.
Further, the molded product of the present invention can be molded by a known method such as injection molding, sheet molding, blow molding, injection blow molding, inflation molding, extrusion molding, foam molding, etc., such as compressed air molding, vacuum molding, etc. Secondary processing and molding methods can also be used.

First, the evaluation methods used in the present invention and examples will be described.
The characteristic evaluation of the resin composition molded article was as follows.
(1) Izod impact strength (with notch)
Testing was performed according to ASDM D256 (notched, 1/8 inch thick).
(2) Molecular weight Using GPC [GPC-8020, manufactured by Tosoh Corporation, detection RI, column Shodex K-805, 801 linked by Showa Denko], the solvent is chloroform, the measurement temperature is 40 ° C., and the weight average molecular weight is calculated in terms of commercially available standard polystyrene. It was.
(3) Optical purity, L-form / D-form composition ratio Hydrolysis with 1N-NaOH aqueous solution using HPLC [LC-10A-VP UV (254 nm) detection manufactured by Shimadzu Corporation] equipped with an optical isomer separation column, HCl Using the aqueous solution neutralized with the sample, the ratio of L-form and D-form was determined.

(4) Tanδ
Using a dynamic viscoelasticity measuring device (DVE-V4 manufactured by Rheo Spector), Tan δ of the injection-molded test piece was measured under the conditions of a frequency of 10 Hz and a heating rate of 3 ° C./min.
(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 characteristics of the block copolymer used as the conjugated diene polymer were evaluated as follows.
(6) Styrene content It computed from the absorption intensity of 262 nm using the ultraviolet spectrophotometer (Hitachi UV200).

(7) 1,2 bond amount and hydrogenation rate Measured using a nuclear magnetic resonance apparatus (DPX-400 manufactured by BRUCKER).
(8) Number average molecular weight of styrene homopolymer block: Method of oxidatively decomposing a block copolymer with ditertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et al., J. 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 the component was determined by GPC measurement. .

(9) Styrene homopolymer block content (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
Polylactic acid-based resins used in the following examples are known, for example, “Polylactide” written by Hidehito Tsuji in Biopolymers Vol. 4 (Wiley-VCH 2002 publication) P129-178 and the special table H05-504731 The polylactic acid-type resin (A-1) was prepared by the ring-opening polymerization method of the lactide using the tin-type catalyst.
The weight average molecular weight, D-form content, and melting point of (A-1) were 170,000, 1.6%, and 164 ° C., respectively.

Furthermore, the manufacture example of the conjugated diene type polymer used for the following example is described.
(Production Example 1) Conjugated diene polymer (B-1)
The autoclave with a stirrer and jacket was washed, dried, purged with nitrogen, charged with a cyclohexane solution (concentration 15% by weight) containing 85 parts by weight of pre-purified butadiene, and then n-butyllithium 1 using tetrahydrofuran After adding 1.5 moles to moles, 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 block 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 1290,000.
The crystal nucleating agent (C-1) used in the examples is shown below.
C-1: Fine talc P-3 manufactured by Nippon Talc

[Example 1]
The composition having the composition shown in Table 1 was melt-kneaded at 190 ° C. using a 25 mm twin-screw extruder (ZSK25 manufactured by Werner & Pfleiderer). The obtained pellets were molded into test pieces using an injection molding machine at a cylinder temperature of 190 ° C., a mold temperature of 30 ° C., and a holding time in the mold of 30 seconds. The obtained test piece was heat-treated for 30 minutes under hot air at 120 ° C. and evaluated. The results are shown in Table 1.

[Example 2]
The composition having the composition shown in Table 1 was melt-kneaded at 190 ° C. using a 25 mm twin-screw extruder (ZSK25 manufactured by Werner & Pfleiderer). The obtained pellets were molded into test pieces using an injection molding machine at a cylinder temperature of 190 ° C., a mold temperature of 100 ° C., and a holding time in the mold of 160 seconds, and evaluated. The results are shown in Table 1.

[Example 3]
Evaluation was performed in the same manner as in Example 2 except that the mold temperature was changed to 110 ° C. The results are shown in Table 1.

[Example 4]
Evaluation was performed in the same manner as in Example 2 except that the mold temperature was set to 116 ° C. The results are shown in Table 1.

[Comparative Example 1]
The composition having the composition shown in Table 1 was melt-kneaded at 190 ° C. using a 25 mm twin-screw extruder (ZSK25 manufactured by Werner & Pfleiderer). The obtained pellets were molded into a test piece by using an injection molding machine at a cylinder temperature of 190 ° C., a mold temperature of 30 ° C., and a holding time in the mold of 30 seconds for evaluation. The results are shown in Table 1.

  The molded body of the present invention is a molded body having excellent impact 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 the automotive field, electrical / electronic field, packaging field, agricultural field, fishery field, medical field, and other general goods. 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. In home appliances and electronic applications, it can be used effectively for electronic devices such as mobile phones and personal computers, housings for home appliances, and LCD front covers. In the packaging field, various types of packaging are possible as films and sheets. In the field, it can be used as a medical material.

6 is a schematic diagram of Tan δ in Examples 1 and 4. FIG.

Claims (14)

A molded article obtained by molding an aliphatic polyester resin composition comprising an aliphatic polyester (a) and an elastic polymer (b), and that the relationship between Tan δ at 80 ° C. and Tan δ at 65 ° C. satisfies the following formula: Characteristic molded product.
Tan δ (80) / Tan δ (65)> 1.00
Tan δ (80): Tan δ of the molded body at 80 ° C.
Tan δ (65): Tan δ of the molded body at 65 ° C.   (B) The component is an elastic polymer 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 molded product according to claim 1.   (B) 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, and its terminal is modified. The molded body according to claim 1, wherein the molded body is a combined body.   The molded product according to claim 1, wherein the polar group is an amino group and / or an imino group.   The molded article according to any one of claims 1 to 4, wherein the component (b) is a modified polymer modified with a modifier having an imidazolidinone skeleton.   Component (b) is a modifier in which an atomic group having a functional group is bonded to the living terminal of a conjugated diene polymer obtained by polymerizing an organolithium compound as a polymerization initiator, or an atomic group in which the functional group is protected. It is an elastic polymer obtained by reacting a modifying agent, or an elastic polymer modified by reacting with a first functional group with a secondary modifier having another functional group. The molded object in any one of 1-5.   The molded product according to any one of claims 1 to 6, wherein the component (b) is an elastic polymer in which a homopolymer of a conjugated diene and / or a copolymer of a conjugated diene and a vinyl aromatic compound is modified.   The component (b) is an elastic polymer in which a copolymer composed of at least one vinyl aromatic compound-based block and at least one conjugated diene-based block is modified. The molded body according to any one of claims 1 to 7.   The molded product according to claim 1, wherein the component (b) is an elastic polymer in which a hydrogenated polymer is modified.   The molded product according to any one of claims 1 to 9, wherein the composition is a composition comprising 60 to 99.9 parts by weight of component (a) and 0.1 to 40 parts by weight of component (b). .   The molded article according to any one of claims 1 to 10, wherein the composition further comprises a crystal nucleating agent (c) component.   The molded body according to claim 11, wherein the composition contains 1 to 50 parts by weight of the component (c) with respect to 100 parts by weight of the component (a) and the component (b).   The molded body according to claim 1, wherein the molded body is injection-molded.   (A) Component is polylactic acid-type resin, The molded object in any one of Claims 1-13 characterized by the above-mentioned.

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