JP2006348159A - Polylactic acid-based resin composition, molded product thereof, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polylactic acid-based resin composition improved in a crystallization rate, having excellent moldability and heat resistance, and improved in impact resistance, and to provide a molded product. <P>SOLUTION: This polylactic acid-based resin composition contains (A) a polylactic acid-based resin, (B) a trimesic acid triamide compound, and (C) an ether ester having a specified structure, and further contains (D) a carbodiimide compound which is used when necessary. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polylactic acid resin composition, a molded body thereof, and a method for producing them.

  In recent years, environmentally friendly plastics for resource recycling have attracted attention. One of them is polylactic acid resin. Since polylactic acid-based resins can be obtained from plants, carbon-neutral materials that do not use petroleum resources and sustainable resources that can contribute to the establishment of a recycling-oriented society are in the spotlight. Polylactic acid-based resins have higher biodegradability than other resins and are expected to be widely used in a wide range of fields as environmentally friendly resins.

  By the way, since the polylactic acid resin generally has a low crystallization speed, it takes a long time to crystallize the polylactic acid resin for the purpose of improving the heat resistance, so that the productivity is poor. When forming into a product exposed to a relatively high temperature, such as tableware, a cup or a home appliance without performing sufficient crystallization, the product (molded product) has a problem of causing thermal deformation and the like. As a means to solve such problems, a technology for blending an inorganic nucleating agent such as talc, mica and calcium carbonate with a polylactic acid resin, or a technology for improving the crystallization speed by blending an organic nucleating agent Is known (see Patent Document 1). However, the addition of an inorganic nucleating agent has a problem that the fluidity of the resin is lowered during molding and the moldability is deteriorated.

  In addition, polylactic acid resins generally have hard and brittle physical properties. A technique of adding a plasticizer to a polylactic acid resin for the purpose of improving such physical properties is known. It is also known that when a plasticizer is further blended with a polylactic acid resin blended with an organic nucleating agent, the crystallization speed is increased (see Patent Document 2). However, further improvement in the crystallization speed is required from the viewpoint of suppressing decomposition of the resin and shortening the molding cycle. On the other hand, it is generally known that in a crystalline resin, impact strength tends to decrease as crystallization progresses and crystallinity increases. Even in a polylactic acid-based resin, it has been difficult to increase the crystallinity and impart heat resistance and at the same time impart impact resistance.

Japanese Patent Laid-Open No. 10-87975 International Publication No. 03/042302 Pamphlet

  In view of the above circumstances, the problem to be solved by the present invention is to obtain a molded article having a sufficiently high crystallization rate, good moldability, and excellent heat resistance and impact resistance by ordinary molding. A polylactic acid-based resin composition that can be used and a molded body that is excellent in heat resistance and impact resistance using the polylactic acid-based resin composition, and a molded body that is excellent in heat resistance and impact resistance. It is to provide a method of manufacturing.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have shown that good moldability is obtained by adding a specific trimesic acid triamide compound and a specific ether ester to a polylactic acid resin, and crystallization is achieved. It can be a resin composition that has a high speed and can greatly improve the heat resistance and impact resistance of the molded product, and further, by molding in a state where the trimesic acid triamide compound is completely dissolved in the resin composition. The present inventors have found that a resin molded body can be obtained in which the crystallization speed is further increased and the molded body has excellent heat resistance and impact resistance, and the present invention has been completed.

［式中、Ｒ^１はトリメシン酸から全てのカルボキシル基を除いて得られる残基を表す。３個のＲ^２は同一又は相異なって、炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基を１〜３個有していてもよいシクロヘキシル基、又は炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基を表す。］
で表される少なくとも１種であり、且つ
（Ｃ）エーテルエステルが、一般式（２）

［式中、Ｒ^３は、炭素数１〜７の直鎖状アルキレン基を表す。Ｒ^４及びＲ^５は同一又は相異なって、炭素数１〜１０の直鎖状若しくは分岐鎖状のアルキル基、炭素数６〜１２のアリール基、炭素数７〜１５のアリールアルキル基、又は炭素数７〜１５のアルキルアリール基を表す。Ｒ^６及びＲ^７は同一又は相異なって炭素数２〜４の直鎖状若しくは分岐鎖状のアルキレン基を表す。ｍ及びｎは、それぞれ０〜８の整数を表し、且つｍ＋ｎの合計は１〜１６の整数を表す。］
で表される少なくとも１種であることを特徴とするポリ乳酸系樹脂組成物。 [Item 1] A polylactic acid resin composition comprising (A) a polylactic acid resin, (B) a trimesic acid triamide compound, and (C) an ether ester,
(B) The trimesic acid triamide compound has the general formula (1)

[Wherein R ¹ represents a residue obtained by removing all carboxyl groups from trimesic acid. Three R ^{2 s} are the same or different and are each a cyclohexyl group optionally having 1 to 3 linear or branched alkyl groups having 1 to 4 carbon atoms, or a straight chain having 1 to 4 carbon atoms. Represents a chain or branched alkyl group. ]
And (C) an ether ester is represented by the general formula (2)

[Wherein R ³ represents a linear alkylene group having 1 to 7 carbon atoms. R ⁴ and R ⁵ are the same or different and are each a linear or branched alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, or carbon The alkylaryl group of several 7-15 is represented. R ⁶ and R ⁷ are the same or different and represent a linear or branched alkylene group having 2 to 4 carbon atoms. m and n represent the integer of 0-8, respectively, and the sum total of m + n represents the integer of 1-16. ]
A polylactic acid-based resin composition, which is at least one kind represented by:

[Item 2] The polylactic acid resin composition according to Item 1, further comprising a carbodiimide compound.

［式中、Ｒ^１は、一般式（１）におけると同義である。Ｒ^５は、炭素数１〜４の直鎖状又は分岐鎖状のアルキル基を表す。ｋは０又は１〜３の整数を表す。］
で表されるトリメシン酸トリアミド化合物である上記項１又は２に記載のポリ乳酸系樹脂組成物。 [Item 3] The trimesic acid triamide compound has the general formula (3):

[Wherein, R ¹ has the same meaning as in general formula (1). R ⁵ represents a linear or branched alkyl group having 1 to 4 carbon atoms. k represents 0 or an integer of 1 to 3. ]
Item 3. The polylactic acid resin composition according to Item 1 or 2, which is a trimesic acid triamide compound represented by the formula:

［式中、Ｒ^９は炭素数２又は４の直鎖状のアルキレン基を表す。Ｒ^１０及びＲ^１１は同一又は相異なって、メチル基、エチル基、ブチル基又はベンジル基を表す。ｈ及びｉは、それぞれ０〜２の整数を表し、且つｈ＋ｉの合計は、２〜４の整数である。］
である上記項１〜３のいずれかに記載のポリ乳酸系樹脂組成物。 [Claim 4]
Ether ester

[Wherein R ⁹ represents a linear alkylene group having 2 or 4 carbon atoms. R ¹⁰ and R ¹¹ are the same or different and each represents a methyl group, an ethyl group, a butyl group or a benzyl group. h and i each represent an integer of 0 to 2, and the sum of h + i is an integer of 2 to 4. ]
The polylactic acid resin composition according to any one of Items 1 to 3, which is

[Item 5] The polylactic acid resin composition according to any one of Items 1 to 4, wherein the content of the trimesic acid triamide compound is 0.05 to 5 parts by weight with respect to 100 parts by weight of the polylactic acid resin. .

CLAIM | ITEM 6 The resin composition in any one of said claim | item 1-5 whose content of ether ester is 1-15 weight part with respect to 100 weight part of polylactic acid-type resin.

[Item 7] The resin composition according to any one of Items 2 to 6, wherein the content of the carbodiimide compound is 0.2 to 5 parts by weight with respect to 100 parts by weight of the polylactic acid resin.

[Item 8] In the polylactic acid-based resin, the proportion of structural units composed of L-lactic acid residues with respect to all the structural units constituting the polylactic acid-based resin is 80 to 99.5 mol%, or the polylactic acid Item 8. The resin composition according to any one of Items 1 to 7, wherein the ratio of the structural unit composed of D-lactic acid residues to all structural units constituting the resin is 80 to 99.5 mol%.

[Item 9] The resin composition according to any one of Items 1 to 8, wherein the acid component content is 5 equivalents / ton or less.

[Item 10] The resin composition according to any one of Items 1 to 9, wherein the crystallization completion time is 90 seconds or less.

[Item 11] A molded article obtained by molding the resin composition according to any one of Items 1 to 10.

[Item 12] A method for producing a polylactic acid resin composition according to any one of Items 1 to 10, wherein (i) (A) a polylactic acid resin, (B) a trimesic acid triamide compound, (C A polylactic acid resin composition characterized by mixing an ether ester and an optionally used (D) carbodiimide compound, or (ii) melting and kneading the mixture at a melting temperature or higher of the polylactic acid resin Manufacturing method.

[Item 13] The process according to Item 12, wherein the trimesic acid triamide compound has an average particle size of 10 μm or less and a maximum particle size of 30 μm or less.

CLAIM | ITEM 14 It is a method of manufacturing a molded object from the resin composition of any one of said claim | item 1-10, Comprising: This resin composition is a melting temperature with respect to molten polylactic acid-type resin of a trimesic-acid triamide compound. At the above temperature, the trimesic acid triamide compound is kneaded until dissolved in the molten polylactic acid resin, and the trimesic acid triamide compound is dissolved in the molten polylactic acid resin and used for the molding step. Manufacturing method of a molded object.

[Item 15] Production of the molded article according to item 14, wherein the molding step is injection molding, extrusion molding, injection blow molding, injection extrusion blow molding, injection compression molding, extrusion blow molding, extrusion thermoform molding, or melt spinning. Method.

  Since the polylactic acid-based resin composition of the present invention has a high crystallization rate and good moldability, a molded article excellent in heat resistance and impact resistance can be obtained in a short time by ordinary molding.

The following is a detailed description of the present invention.
(A) Polylactic acid-based resin The polylactic acid-based resin according to the present invention is not particularly limited, and polylactic acid-based resins having lactic acid units with various optical purities can be used, but structural units composed of L-lactic acid residues ( A so-called L-lactic acid unit) or a structural unit composed of D-lactic acid residues (so-called D-lactic acid unit) is in the range of 80 to 99.5 mol% with respect to all structural units constituting the polylactic acid resin. It is preferable. Such a polylactic acid resin is relatively easy to obtain and has a high melting point, so that it becomes easy to obtain a resin composition having better heat resistance. The structural unit consisting of L-lactic acid residue or D-lactic acid residue is more preferably in the range of 90 to 99.2 mol%, and 93 to 99 mol, based on all structural units constituting the polylactic acid resin. More preferably, it is in the range of%.

  Moreover, what is derived from L-lactic acid, D-lactic acid, DL-lactic acid, L-lactide, D-lactide, meso-lactide alone or a mixture thereof can be used as the polylactic acid resin. That is, it may be produced by direct dehydration condensation of lactic acid or by lactide ring-opening method.

In addition, the polylactic acid-based resin may have other structural units other than lactic acid residues as long as the effects of the present invention are not impaired (the range is preferably 50 mol% or less, more preferably Such other structural units include, for example, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, and ethylene glycol, propylene glycol, 1, 4 -Hydroxycarboxylic acid units derived from aliphatic glycols such as butanediol; units of hydroxycarboxylic acids such as glycolic acid, β-hydroxybutyric acid, hydroxypivalic acid, hydroxyvaleric acid, and the like.
In addition, when the polylactic acid-based resin includes a structural unit derived from a hydroxycarboxylic acid other than lactic acid, the “all structural units constituting the polylactic acid-based resin” in the present invention refers to a structural unit derived from lactic acid (lactic acid Residues) and structural units derived from hydroxycarboxylic acids other than lactic acid.

  In the present invention, the molecular weight of the polylactic acid resin is not particularly limited, but the number average molecular weight (Mn) is preferably in the range of 5,000 to 400,000, and preferably 10,000 to 200,000. More preferred. When the number average molecular weight (Mn) is smaller than 5,000, when a molded product is produced using the obtained resin composition, the strength thereof decreases, the acid component content increases, the hydrolyzability increases, etc. This tends to reduce the stability. On the other hand, when it is larger than 400,000, the moldability tends to deteriorate when the resulting resin composition is molded. In the present invention, the number average molecular weight is a value in terms of polymethyl methacrylate (PMMA) measured by GPC (gel permeation chromatography). As GPC measurement conditions, 150C ALC / GPC manufactured by Waters as a GPC device, Shodex (registered trademark) HFIP806M manufactured by Showa Denko KK as a column, RI detector as a detector, hexafluoro of 20 mM sodium trifluoroacetate as a developing solvent An isopropanol solution is used, the column temperature is 40 ° C., and the flow rate is 1.0 mL / min. Standard PMMA used for PMMA conversion is PM1 manufactured by Polymer Laboratories.

  In addition, the polylactic acid-type resin used by this invention may use what was induced | guided | derived from a plant from the point of availability, L- or D-methyl lactate, L- or D-ethyl lactate. It is also possible to use a product produced from a lactic acid derivative such as a raw material (monomer) or a product produced by a microorganism.

［式中、Ｒ^１はトリメシン酸から全てのカルボキシル基を除いて得られる残基を表す。３個のＲ^２は同一又は相異なって、炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基を１〜３個有していてもよいシクロヘキシル基、又は炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基を表す。］
で表される。 (B) Trimesic acid triamide compound The trimesic acid triamide compound according to the present invention has the general formula (1)

[Wherein R ¹ represents a residue obtained by removing all carboxyl groups from trimesic acid. Three R ^{2 s} are the same or different and are each a cyclohexyl group optionally having 1 to 3 linear or branched alkyl groups having 1 to 4 carbon atoms, or a straight chain having 1 to 4 carbon atoms. Represents a chain or branched alkyl group. ]
It is represented by

  There is no particular limitation on the production method of the trimesic acid triamide compound, for example, trimesic acid or its acid chloride and a cyclohexylamine optionally having a linear or branched alkyl group having 1 to 4 carbon atoms, or It can be obtained by amidating a linear or branched alkylamine having 1 to 4 carbon atoms.

  Specific examples of the cyclohexylamine optionally having a linear or branched alkyl group having 1 to 4 carbon atoms include cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methyl. Cyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4-ethylcyclohexylamine, 2-n-propylcyclohexylamine, 3-n-propylcyclohexylamine, 4-n-propylcyclohexylamine, 2-iso-propyl Cyclohexylamine, 3-iso-propylcyclohexylamine, 4-iso-propylcyclohexylamine, 2-n-butylcyclohexylamine, 3-n-butylcyclohexylamine, 4-n-butylcyclohexylamine, -Iso-butylcyclohexylamine, 3-iso-butylcyclohexylamine, 4-iso-butylcyclohexylamine, 2-sec-butylcyclohexylamine, 3-sec-butylcyclohexylamine, 4-sec-butylcyclohexylamine, 2-tert -Butylcyclohexylamine, 3-tert-butylcyclohexylamine, 4-tert-butylcyclohexylamine, 2,3-dimethylcyclohexylamine, 2,4-dimethylcyclohexylamine, 2,5-dimethylcyclohexylamine, 2,6-dimethyl Cyclohexylamine, 2,3,4-trimethylcyclohexylamine, 2,3,5-trimethylcyclohexylamine, 2,3,6-trimethylcyclohexylamine, 2,4,6-trimethyl Chill cyclohexylamine, 3,4,5-trimethyl cyclohexylamine, and the like. Specific examples of the linear or branched alkylamine having 1 to 4 carbon atoms include methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec-butylamine, tert -Butylamine is mentioned.

［式中、Ｒ^１は、一般式（１）におけると同義である。Ｒ^８は、炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基を表す。ｋは、０又は１〜３の整数を表す。］
で表されるシクロヘキサン環を有するトリアミド化合物が好ましい。この中でも、特に
トリメシン酸トリシクロヘキシルアミド、トリメシン酸トリ（２−メチルシクロヘキシルアミド）、トリメシン酸トリ（３−メチルシクロヘキシルアミド）、トリメシン酸トリ（４−メチルシクロヘキシルアミド）、トリメシン酸トリ（２，３−ジメチルシクロヘキシルアミド）が好ましく、特に、トリメシン酸トリシクロヘキシルアミド、トリメシン酸トリ（２−メチルシクロヘキシルアミド）が好ましい。 Among the above trimesic acid triamide compounds, the compound represented by the general formula (3) is particularly excellent in improving the crystallization speed of the polylactic acid resin.

[Wherein, R ¹ has the same meaning as in general formula (1). R ⁸ represents a linear or branched alkyl group having 1 to 4 carbon atoms. k represents 0 or an integer of 1 to 3. ]
The triamide compound which has a cyclohexane ring represented by these is preferable. Among these, in particular, trimesic acid tricyclohexylamide, trimesic acid tri (2-methylcyclohexylamide), trimesic acid tri (3-methylcyclohexylamide), trimesic acid tri (4-methylcyclohexylamide), trimesic acid tri (2,3 -Dimethylcyclohexylamide) is preferable, and trimesic acid tricyclohexylamide and trimesic acid tri (2-methylcyclohexylamide) are particularly preferable.

  The trimesic acid triamide compounds can be used alone or in admixture of two or more.

  The shape of the trimesic acid triamide compound is not particularly limited, but an average particle size of 10 μm or less and a maximum particle size of 30 μm or less are preferable, and an average particle size of 5 μm or less and a maximum particle size of 20 μm or less are particularly preferable. When the average particle size is larger than 10 μm or the maximum particle size is larger than 30 μm, the dissolution of the trimesic acid triamide compound in the polylactic acid resin is insufficient, and the nucleation action on the polylactic acid resin tends to be reduced. There is. As a result, the relative crystallinity of the obtained molded product is lowered, and the heat resistance tends to be lowered. Here, the maximum particle size means a particle size in which the percentage of the particle amount smaller than the particle size is 99% with respect to the total particle amount when measured by the method described in the examples described later.

  The amount of the trimesic acid triamide compound can be appropriately changed according to the specific application of the resin composition. Generally, 0.05 to 5 parts by weight per 100 parts by weight of the polylactic acid resin is used. Preferably, 0.1-2 weight is more preferable, and 0.2-1.5 weight part is especially preferable. When the amount used is less than 0.05 parts by weight, the effect of improving the crystallization speed tends to be small. On the other hand, when the amount exceeds 5 parts by weight, the effect corresponding to the amount added is not increased, and the cost tends to increase.

  Moreover, you may further add inorganic type nucleating agents, such as a talc, a mica, and a calcium carbonate, as needed within the range which does not impair the effect of this invention. The amount of the inorganic nucleating agent added is preferably 3 to 30 parts by weight with respect to 100 parts by weight of the polylactic acid resin.

［式中、Ｒ^３は、炭素数１〜８の直鎖状アルキレン基を表す。Ｒ^４及びＲ^５は同一又は相異なって、炭素数１〜１０の直鎖状若しくは分岐鎖状のアルキル基、炭素数６〜１２のアリール基、炭素数７〜１５のアリールアルキル基、又は炭素数７〜１５のアルキルアリール基を表す。Ｒ^６及びＲ^７は同一又は相異なって炭素数２〜４の直鎖状若しくは分岐鎖状のアルキレン基を表す。ｍ及びｎは、それぞれ０〜８の整数を表し、且つｍ＋ｎの合計は１〜１６の整数を表す。］
で表される。 (C) Ether Ester The ether ester according to the present invention (hereinafter referred to as “the present ester”) is represented by the general formula (2).

[Wherein R ³ represents a linear alkylene group having 1 to 8 carbon atoms. R ⁴ and R ⁵ are the same or different and are each a linear or branched alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, or carbon The alkylaryl group of several 7-15 is represented. R ⁶ and R ⁷ are the same or different and represent a linear or branched alkylene group having 2 to 4 carbon atoms. m and n represent the integer of 0-8, respectively, and the sum total of m + n represents the integer of 1-16. ]
It is represented by

［式中、Ｒ^３は一般式（２）におけると同義である。］
で表される脂肪族二塩基酸及び、これらのエステル形成性誘導体（例えば、酸無水物、酸塩化物、メチルエステル、エチルエステルン等の低級エステル）が例示される。具体的には、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸及びこれらのエステル形成性誘導体が挙げられる。これらの中でも、ポリ乳酸系樹脂との相溶性の点から、コハク酸、アジピン酸が好ましく、特にアジピン酸が推奨される。 There is no limitation in the manufacturing method of this ester, For example, it can obtain by esterifying a corresponding acid component and a monohydric alcohol component.
As an acid component, general formula (5)

[Wherein R ³ has the same meaning as in general formula (2). ]
And ester-forming derivatives thereof (for example, lower esters such as acid anhydrides, acid chlorides, methyl esters, and ethyl esters). Specific examples include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and ester-forming derivatives thereof. Among these, succinic acid and adipic acid are preferable from the viewpoint of compatibility with the polylactic acid resin, and adipic acid is particularly recommended.

［式中、Ｒ^１２ は炭素数１〜１０の直鎖状若しくは分岐鎖状のアルキル基、炭素数６〜１２のアリール基、炭素数７〜１５のアリールアルキル基又は炭素数７〜１５のアルキルアリール基を表す。Ｒ^１３は、炭素数２〜４の直鎖状又は分岐鎖状のアルキレン基を表す。ｊは、０又は１〜８の整数を表す。］
で表される一価アルコールが例示される。本エステルは、一般式（６）におけるｊが１〜８である一価アルコールの１種又は２種以上をエステル化反応に供することにより、或いは、該一価アルコールとｊが０である一価アルコールとをアルコール成分として、エステル化反応に供することにより得ることができる。 As a monohydric alcohol component, general formula (6)

[Wherein, R ¹² represents a linear or branched alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, or an alkyl having 7 to 15 carbon atoms. Represents an aryl group. R ¹³ represents a linear or branched alkylene group having 2 to 4 carbon atoms. j represents 0 or an integer of 1 to 8. ]
The monohydric alcohol represented by these is illustrated. The present ester is obtained by subjecting one or more monohydric alcohols having j in the general formula (6) of 1 to 8 to an esterification reaction, or a monovalent alcohol in which j is 0 with the monohydric alcohol. It can be obtained by subjecting alcohol as an alcohol component to an esterification reaction.

Specific examples of R ¹² in the general formula (6) include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, phenyl group, naphthyl group, Methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, methylnaphthyl group, ethylnaphthyl group, propylnaphthyl group, butylnaphthyl group And pentylnaphthyl group, benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group, phenylpentyl group, phenyloctyl group, phenylnonyl group and the like. Specific examples of R ¹³ include ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group and the like.

Among the monohydric alcohol components, R ¹² in the general formula (6) is a linear or branched alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 to 10 carbon atoms. It is preferably an alkylaryl group or an arylalkyl having 7 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms or a benzyl group, and particularly a methyl group, an ethyl group, a butyl group or a benzyl group. preferable. R ¹³ preferably has an ethylene group or a 1,2-propylene group, and particularly preferably an ethylene group. j is preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 2.

  Specific examples of particularly preferred monohydric alcohol components include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, and one or two of these (particularly two), or It is preferable to use benzyl alcohol in combination for the esterification reaction.

Preferred specific examples of the ester include di (methoxyethoxyethyl) = succinate,
Di (ethoxyethoxyethyl) = succinate, di (propoxyethoxyethyl) = succinate, di (butoxyethoxyethyl) = succinate, di (methoxyethoxyethyl) = adipate, di (ethoxyethoxyethyl) = adipate, di (propoxyethoxyethyl) ) = Adipate, di (butoxyethoxyethyl) = adipate, methoxyethoxyethyl = ethoxyethoxyethyl = succinate, methoxyethoxyethyl = propoxyethoxyethyl = succinate, methoxyethoxyethyl = butoxyethoxyethyl = succinate, methoxyethoxyethyl = benzyl = succinate Ethoxyethoxyethyl = propoxyethoxyethyl = succinate, ethoxyethoxyethyl = butoxyethoxyethyl = succinate, Toxiethoxyethyl = benzyl = succinate, propoxyethoxyethyl = butoxyethoxyethyl = succinate, propoxyethoxyethyl = benzyl = succinate, butoxyethoxyethyl = pentyl = succinate, methoxyethoxyethyl = ethoxyethoxyethyl = adipate, methoxyethoxyethyl = propoxyethoxy Ethyl adipate, methoxyethoxyethyl = butoxyethoxyethyl = adipate, methoxyethoxyethyl = benzyl = adipate, ethoxyethoxyethyl = propoxyethoxyethyl = adipate, ethoxyethoxyethyl = butoxyethoxyethyl = adipate, ethoxyethoxyethyl = benzyl = adipate, Propoxyethoxyethyl = butoxyethoxyethyl = adipate Propoxy ethoxyethyl = benzyl = adipates include butoxyethoxyethyl = Penjiru = adipate. Of these, adipic acid ester compounds are preferred, and in particular, methoxyethoxyethyl = ethoxyethoxyethyl = adipate, methoxyethoxyethyl = propoxyethoxyethyl = adipate, methoxyethoxyethyl = butoxyethoxyethyl = adipate, methoxyethoxyethyl = benzyl = adipate, ethoxy Ethoxyethyl = benzyl = adipate and butoxyethoxyethyl = pentyl = adipate are preferred.

(D) Carbodiimide compound The resin composition of this invention can contain a carbodiimide compound as needed. In the present invention, the carbodiimide compound exhibits an effect of suppressing hydrolysis of the polylactic acid resin by cross-linking reaction with the terminal carboxylic acid of the polylactic acid resin. The carbodiimide compound is not particularly limited as long as it has one or more carbodiimide groups in the molecule. For example, a carbodiimide compound synthesized by a decarboxylation reaction from an isocyanate compound according to a conventionally known method can be used. Moreover, you may use what is marketed. Examples of the monocarbodiimide compound having one carbodiimide group in the molecule include aliphatic or alicyclic monocarbodiimides such as diisopropylcarbodiimide, dicyclohexylcarbodiimide and dioctylcarbodiimide, and aromatic monocarbodiimides such as diphenylcarbodiimide. As an isocyanate compound in the synthesis of a polycarbodiimide having two or more carbodiimide groups in the molecule, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2 Aromatic diisocyanates such as 1,4-tolylene diisocyanate, tetramethylxylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate; Nert, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, etc. Aliphatic or Alicyclic diisocyanate and the like. The polycarbodiimide may have all or part of the isocyanate group remaining at the end sealed, and as such a sealing agent, monoisocyanate such as cyclohexyl isocyanate, phenyl isocyanate, tolyl isocyanate, etc. Compound: Compounds having active hydrogen such as hydroxyl group and amino group are exemplified. Among the carbodiimide compounds, polycarbodiimide having two or more carbodiimide groups in the molecule is preferable from the viewpoint of improving hydrolysis resistance of a molded product molded from the obtained resin composition. Polycarbodiimide obtained from aliphatic or alicyclic carbodiimide, aliphatic or alicyclic diisocyanate is preferable from the viewpoint of the compatibility of the above and the hydrolysis resistance of a molded product molded from the resulting resin composition. In the present invention, as the carbodiimide compound, one or more kinds of compounds can be used.

  When the carbodiimide compound is used, it can be appropriately changed according to each application, but is preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the polylactic acid resin used, More preferably, it is -2.5 weight part.

  Although the acid component content of the resin composition of the present invention can be appropriately changed according to each application, it becomes easy to obtain a resin composition having higher stability. Or less, more preferably 0 equivalent / ton or more and 1 equivalent / ton or less. The acid component content can be adjusted, for example, by changing the amount and type of the carbodiimide compound described above. The acid component content varies depending on the carboxyl group terminal concentration of the polylactic acid resin in the resin composition of the present invention, the concentration of acidic functional groups contained in optional components, and the like. The acid component content can be determined by a titration method as described in Examples described later.

  The resin composition of the present invention contains an inorganic additive such as dibasic sulfate, dibasic lead stearate, calcium hydroxide, calcium silicate, etc., as necessary within the range not impairing the effects of the present invention; , Pigments, impact resistance improvers, processing aids, reinforcing agents, colorants, flame retardants, weather resistance improvers, UV absorbers, antioxidants, hydrolysis resistance improvers, fungicides, antibacterial agents, light Various additives such as stabilizers, anti-static agents, silicone oil, anti-blocking agents, mold release agents, foaming agents, and fragrances; various fibers such as glass fibers and polyester fibers; fillers such as silica and wood flour; various couplings Arbitrary components, such as an agent, can be mix | blended as needed.

  Furthermore, the resin composition of the present invention can be used as necessary within the range not impairing the effects of the present invention. Polyurethane resin; Polyamide resin; Polyester resin; Polyvinyl chloride resin; Polyvinylidene chloride resin; Polycarbonate resin; Resin; Saponified ethylene-vinyl acetate copolymer; Acrylic resin such as polyacrylate, polymethacrylate, polymethyl methacrylate, methyl methacrylate-acrylic ester copolymer; Copolymerization of aromatic vinyl compound and vinyl cyanide compound Polymer; aromatic vinyl compound-vinyl cyanide compound-olefin compound copolymer; methyl methacrylate-styrene-butylene copolymer; other resins such as styrene polymer and olefin polymer may be contained. .

Polylactic acid resin composition and production method thereof The resin composition of the present invention can be obtained by kneading the above components. There is no restriction | limiting in particular as the kneading | mixing method of each component, It can mix by a conventionally well-known method. For example, a dry blend method in which each component is charged and mixed in a tumbler, V-type blender, ribbon blender, Hell shell mixer, tumbler mixer, etc. The method of melt-kneading above the melting temperature of lactic acid-type resin, cooling, and pelletizing is mentioned. Moreover, the solution blend method etc. which dissolve each resin in a solvent and remove a solvent after mixing are mentioned.

  In particular, in the method for producing a polylactic acid resin composition of the present invention, the trimesic acid triamide compound has an average particle size of 10 μm or less and a maximum particle size of 30 μm or less, preferably an average particle size of 5 μm or less and a maximum particle size of 20 μm. By using the following trimesic acid triamide, the crystallization speed of the resin composition is increased, and as a result, a molded article having a high relative crystallinity is easily obtained even in a short molding time. Such a molded body having a high relative crystallinity is preferable because the heat resistance is improved.

The crystallization completion time of the resin composition of the present invention is preferably 90 seconds or shorter, and more preferably 50 seconds or shorter. When the crystallization completion time is in this range, a molded product having high heat resistance can be easily obtained in a shorter time by a normal molding method when the resin composition is molded. The crystallization completion time of the resin composition can be adjusted by increasing or decreasing the amounts of the trimesic acid triamide compound and ether ester used in the present invention.
In the present specification, the crystallization completion time is a time until completion of heat generation due to crystallization, which is measured by a differential scanning calorimeter (DSC).

Polylactic acid-based resin molded body and method for producing the same The resin composition of the present invention is easily molded into molded bodies of various shapes by known molding methods such as extrusion molding, injection molding, calendar molding, vacuum molding, and pressure molding. In addition, the molded product obtained can be a molded product having excellent heat resistance and impact resistance. This effect is an effect that appears remarkably when the trimesic acid triamide compound according to the present invention is used in combination with an ether ester. It can also be formed into a fiber by melt spinning.

  Furthermore, by molding the resin composition of the present invention in accordance with the method for producing a molded article of the present invention, a molded article having excellent heat resistance and good impact resistance can be obtained in a short time. The method for producing such a molded article is to set the resin temperature at a temperature equal to or higher than the melting temperature of the trimesic acid triamide compound in the molten polylactic acid resin, and knead until the trimesic acid triamide compound is dissolved in the molten polylactic acid resin. The trimesic acid triamide compound is characterized in that it is subjected to a molding step in a state dissolved in a molten polylactic acid-based resin, thereby giving a high relative crystallinity to the molded body in a short molding time, Excellent heat resistance and impact strength can be imparted. The relative degree of crystallinity is a value measured by the method described in Examples described later.

Since the trimesic acid triamide compound generally has a high melting point of about 180 ° C. to 380 ° C., it is higher than the melting point of the polylactic acid resin (generally 145 ° C. to 180 ° C.). The system resin is melted first, and then the trimesic acid triamide compound is dissolved in the molten polylactic acid resin. Therefore, in this specification, the “dissolution temperature” of the trimesic acid triamide compound in the molten polylactic acid resin is obtained by heating the resin composition (pellet or dry blend) containing the trimesic acid triamide compound under an optical microscope. The temperature at which the trimesic acid triamide compound is dissolved in the molten polylactic acid resin and no solid is observed. In addition, in the case of injection molding, whether or not the trimesic acid triamide compound is dissolved in the molten polylactic acid resin can be easily determined by visually observing the molten resin composition coming out from the nozzle tip of the heating cylinder. Can do. That is, the trimesic acid triamide compound is not completely dissolved in the molten polylactic acid-based resin, and if any solid remains, the molten resin composition is cloudy, but if completely dissolved, it becomes cloudy. It is not transparent. Similarly, in extrusion molding, it can be confirmed whether or not the molten resin composition is completely dissolved by visual observation of the transparency of the molten resin composition discharged from the die. In the case of other molding methods, it can be confirmed in the molding step whether the molten resin composition discharged from the cylinder nozzle or the die is completely dissolved by visual observation.
The dissolution temperature depends on the type, particle size and amount of the trimesic acid triamide compound, the type of polylactic acid resin, the type and amount of carbodiimide compound, and the type and amount of ether ester. Although it varies, the trimesic acid triamide compound is usually in the range of 210 ° C to 250 ° C in the range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the polylactic acid resin. Therefore, in the range of the above addition amount, it is preferable to knead at a temperature of 220 ° C. to 245 ° C. from the balance of 210 ° C. to 250 ° C. and thermal decomposition suppression of the polylactic acid resin.
Further, kneading so that the solid trimesic acid triamide compound does not exist can be performed by adjusting the residence time of the resin composition during heating and melting, the screw rotation speed, and the like. Next, while maintaining this molten state, the resin composition is subjected to a molding step to cool and crystallize the resin composition. The temperature during cooling (for example, the mold temperature in injection molding) is preferably 60 to 120 ° C, particularly 90 to 110 ° C. The cooling time is exemplified by 1 to 180 seconds, preferably 5 to 120 seconds, and particularly preferably 10 to 90 seconds. As the cooling time is shorter, the productivity is improved and the residence time of the resin composition inside the cylinder is shorter, so that the decomposition of the resin can be suppressed. By using such a molding method, it is possible to obtain a molded article having a high crystallization rate and excellent moldability, and having a high relative crystallinity, a heat resistant temperature, and a high impact strength. In particular, when the molding method is a molding method including an injection process such as injection molding, injection blow molding, injection compression molding, or melt spinning molding, the effect of the production method of the present invention tends to be easily obtained.

The molded body thus obtained varies depending on the type of resin, the blending amount of each component, the molding method, and the like, but the relative crystallinity is exemplified by 85 to 100%, particularly preferably 95 to 100%.
Examples of the heat resistant temperature include 90 to 120 ° C, and 110 to 120 ° C is particularly preferable. Moreover, as surface impact strength (breaking energy), 2.0-3.2J is illustrated, and 2.6-3.2J is especially preferable. Moreover, 80-100% is illustrated as an intensity | strength retention rate at the time of using a carbodiimide compound, and 84-100% is especially preferable.

  The molded body of the present invention is, for example, a vehicle part, a housing such as a body of a household appliance, a gear, general goods, clothing, a bag, a latch member such as a fastener or a button, agricultural material, building material, civil engineering material, tableware. It can be suitably used as a kind or toy.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Measurement methods and chemicals used in the following examples and comparative examples are as follows.

<Measurement method>
Particle size of organic nucleating agent: Non-ionic surfactant (Triton X-100) was dissolved using a laser diffraction scattering method particle size distribution measuring device (Microtrac particle size distribution device FRA). After dispersing the organic nucleating agent in water and ultrasonically dispersing for 3 minutes, the particle size distribution was measured.

  Acid component content: A 100 mL Erlenmeyer flask was dissolved in a resin composition (0.5 g) and chloroform (50 mL) after blast drying at 100 ° C. for 12 hours. To this was further added benzyl alcohol (50 mL). The solution was titrated with a 0.005N potassium hydroxide / ethanol solution using phenolphthalein as an indicator to obtain a titer. Separately, a blank test without using a resin composition was performed to obtain a titer. The acid component content was calculated from both titration amounts.

  Crystallization completion time: Using a differential scanning calorimeter (Perkin Elmer, DSC7), the resin composition (10 mg) was melted at 220 ° C. for 2 minutes, and further, 100 ° C. at a rate of −70 ° C./min. Then, the temperature was kept at 100 ° C., and the calorific value with respect to time was measured. Based on the time when the temperature reached 100 ° C., the time to complete the exotherm (the time until the exothermic peak returned to the baseline) was defined as the crystallization completion time.

Relative crystallinity: Using a differential scanning calorimeter (Perkin Elmer, DSC7), test pieces (thickness 4 mm) obtained in the following examples and comparative examples were cut to obtain evaluation samples. When about 10 mg of the evaluation sample was heated from 20 ° C. to 200 ° C. at a rate of 10 ° C./min, the heat of crystallization ΔHc (J / g) and the heat of fusion ΔHm (J / g) were measured, and the relative crystal The degree of conversion was calculated from the following formula.
Relative crystallinity (%) = (ΔHm−ΔHc) / ΔHm × 100

Formability: Formability when producing test pieces (thickness 2 mm) in the following examples and comparative examples was evaluated according to the following criteria.
A: Good releasability and easy molding.
○: Slightly attached to the mold, but relatively easy to mold.
X: Molding is difficult due to poor releasability from the mold.

  Heat-resistant temperature: The deflection temperature under load (HDT) was measured for test pieces (thickness 4 mm) obtained in the following examples and comparative examples according to JIS K-7191. The temperature obtained by this was defined as the heat resistant temperature.

  Surface impact strength: The surface impact strength of a test piece (thickness 2 mm) obtained in each of the following Examples and Comparative Examples was measured at 23 ° C. by a falling weight impact test according to JIS K-7221. A weight having a tip radius of 1/4 inch was used. The 50% fracture energy obtained in this way was defined as the surface impact strength. The larger this value, the better the impact resistance.

Strength retention: Test pieces (thickness 2 mm) obtained in the following examples and comparative examples were left for 30 hours under conditions of a temperature of 80 ° C. and a humidity of 95% Rh. Tensile strength (measurement conforms to JIS K-7113) was measured before and after standing, and the strength retention was calculated by the following formula.
Strength retention (%) = (Tensile strength after leaving) / (Tensile strength before leaving) × 100

<Used chemicals>
(Polylactic acid resin)
Polylactic acid resin: Cargill Dow (# 3001D) (content of structural unit consisting of L-lactic acid residue: 98.5 mol%, number average molecular weight (Mn: 150,000))
(Trimesic acid triamide compound)
Trimesic acid triamide A: trimesic acid tricyclohexylamide (average particle size 1.6 μm, maximum particle size 10 μm): manufactured by Shin Nippon Rika Co., Ltd. (NJESTA-TF-1)
Trimesic acid triamide B: Trimesic acid tri (2-methylcyclohexylamide) (average particle size 1.5 μm, maximum particle size 10 μm): Shin Nippon Rika Co., Ltd. (nucleating agent MF)
(Inorganic nucleating agent C)
Talc (average particle size 4.0 μm): manufactured by Nippon Talc Co., Ltd. (Microace P-6)
(Ether ester D)
Methoxyethoxyethyl = Pendyl = Adipate (ether ester E)
Butoxyethoxyethyl = benzyl = adipate (ether ester F)
Methoxyethoxyethyl = butoxyethoxyethyl = adipate (plasticizer G)
Polyethylene glycol (average molecular weight 200) dibenzoate: manufactured by Shin Nippon Rika Co., Ltd. (Likaflow LA-100)
(Stabilizer H)
Polycarbodiimide: Nisshinbo Co., Ltd. (carbodilite LA-1)

<Example 1>
A polylactic acid resin (100 parts by weight), trimesic acid triamide A (1 part by weight), ether ester D (5 parts by weight) and stabilizer H (polycarbodiimide) (1 part by weight) are dry blended to obtain a resin composition. Obtained. The resin composition (dry blend) is melt-kneaded at 220 to 250 ° C., and when the acid component content becomes 1.0 equivalent / ton or less, it is extruded into water as a strand, cut with a pelletizer, and pellets Got. Next, the pellets were dried in a vacuum dryer at 80 ° C. for 12 hours, and then each test with a thickness of 4 mm and 2 mm was performed with an injection molding machine set at a resin temperature of 235 ° C. and a mold temperature of 100 ° C. with a cooling time of 30 seconds. A piece was formed. Table 1 below summarizes the moldability during molding of the test piece, the heat-resistant temperature, the relative crystallinity, the surface impact strength, and the strength retention of the test piece. Note that the trimesic acid tricyclohexylamide is completely dissolved in the molten polylactic acid-based resin when the test piece is manufactured. This means that the molten resin coming from the nozzle tip of the heating cylinder of the injection molding machine is transparent. This was confirmed by visual observation.

<Examples 2 to 8>
A test piece was produced in the same manner as in Example 1 except that the resin composition shown in Table 1 was used. Table 1 below summarizes the moldability during molding of the test piece, the heat-resistant temperature, the relative crystallinity, the surface impact strength, and the strength retention of the test piece. In any test piece production, the trimesic acid triamide compound is completely dissolved in the molten polylactic acid resin. The molten resin coming out from the nozzle tip of the heating cylinder of the injection molding machine is transparent. This was confirmed by visual observation.

<Examples 9 and 10>
A test piece was prepared in the same manner as in Example 1 except that the resin composition shown in Table 1 was used and the resin temperature during injection molding was 195 ° C. Table 1 below summarizes the moldability during molding of the test piece, the heat-resistant temperature, the relative crystallinity, the surface impact strength, and the strength retention of the test piece. It should be noted that the trimesic acid triamide compound is not completely dissolved in the molten polylactic acid resin when the test piece is produced, and the molten resin coming out from the nozzle tip of the heating cylinder of the injection molding machine is slightly cloudy. This was confirmed by visual observation.

<Comparative Example 1>
A test piece was prepared in the same manner as in Example 1 except that the plasticizer G “polyethylene glycol (average molecular weight 200) dibenzoate” was used in place of the ether ester D. Table 1 below summarizes the moldability during molding of the test piece, the heat-resistant temperature, the relative crystallinity, the surface impact strength, and the strength retention of the test piece.

<Comparative Example 2>
A test piece was prepared according to the same method as in Example 1 except that no ether ester was used and the cooling time during injection molding was set to 60 seconds. The mold releasability from the mold during molding was poor, and deformations such as protrusions were observed in the obtained test piece. The heat resistance temperature, relative crystallinity, surface impact strength, and strength retention of the test piece are summarized in Table 1 below.

<Comparative Example 3>
A test piece was produced in the same manner as in Example 1 except that trimesic acid triamide was not used and the cooling time at the time of injection molding was set to 60 seconds. The mold releasability from the mold during molding was poor, and deformations such as protrusions were observed in the obtained test piece. The heat resistance temperature, relative crystallinity, surface impact strength, and strength retention of the test piece are summarized in Table 1 below.

<Comparative Example 4>
A test piece was prepared in the same manner as in Example 1 except that the inorganic nucleating agent C (talc) was used instead of trimesic acid triamide and the cooling time at the time of injection molding was set to 60 seconds. The mold releasability from the mold during molding was poor, and deformations such as protrusions were observed in the obtained test piece. The heat resistance temperature, relative crystallinity, surface impact strength, and strength retention of the test piece are summarized in Table 1 below.

<Comparative Example 5>
Using only a polylactic acid resin, test pieces having a thickness of 4 mm and 2 mm were produced with an injection molding machine set at a molten resin temperature of 235 ° C. and a mold temperature of 100 ° C. with a cooling time of 60 seconds. The mold releasability from the mold during molding was poor, and deformations such as protrusions were observed in the obtained test piece. The heat resistance temperature, relative crystallinity, surface impact strength, and strength retention of the test piece are summarized in Table 1 below.

<Comparative Example 6>
A test piece made of only a polylactic acid resin was produced in the same manner as in Comparative Example 6 except that the mold temperature was changed from 100 ° C. to 30 ° C. Table 1 below summarizes the moldability during molding of the test piece, the heat-resistant temperature, the relative crystallinity, the surface impact strength, and the strength retention of the test piece.

As is apparent from Table 1, the polylactic acid resin composition using the trimesic acid triamide compound and the ether ester has a short crystallization completion time, so that the moldability is good, the relative crystallinity is high, and the heat resistance is excellent. At the same time, a molded article excellent in impact resistance can be obtained.
On the other hand, when the ether ester is not used, the crystallization completion time becomes longer and the impact resistance is lowered. (Comparative Examples 1 and 2). When the trimesic acid triamide compound is not used, both the crystallization completion time and the relative crystallinity are remarkably reduced (Comparative Examples 3 and 4).

Claims (15)

A polylactic acid resin composition comprising (A) a polylactic acid resin, (B) a trimesic acid triamide compound, and (C) an ether ester,
(B) The trimesic acid triamide compound has the general formula (1)

[Wherein R ¹ represents a residue obtained by removing all carboxyl groups from trimesic acid. Three R ^{2 s} are the same or different and are each a cyclohexyl group optionally having 1 to 3 linear or branched alkyl groups having 1 to 4 carbon atoms, or a straight chain having 1 to 4 carbon atoms. Represents a chain or branched alkyl group. ]
And (C) an ether ester is represented by the general formula (2)

[Wherein R ³ represents a linear alkylene group having 1 to 8 carbon atoms. R ⁴ and R ⁵ are the same or different and are each a linear or branched alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, or carbon The alkylaryl group of several 7-15 is represented. R ⁶ and R ⁷ are the same or different and represent a linear or branched alkylene group having 2 to 4 carbon atoms. m and n represent the integer of 0-8, respectively, and the sum total of m + n represents the integer of 1-16. ]
A polylactic acid-based resin composition, which is at least one kind represented by:   Furthermore, the polylactic acid-type resin composition of Claim 1 containing a carbodiimide compound. The trimesic acid triamide compound has the general formula (3)

[Wherein, R ¹ has the same meaning as in general formula (1). R ⁸ represents a linear or branched alkyl group having 1 to 4 carbon atoms. k represents 0 or an integer of 1 to 3. ]
The polylactic acid resin composition according to claim 1, which is a trimesic acid triamide compound represented by the formula: Ether ester

[Wherein R ⁹ represents a linear alkylene group having 2 or 4 carbon atoms. R ¹⁰ and R ¹¹ are the same or different and each represents a methyl group, an ethyl group, a butyl group or a benzyl group. h and i each represent an integer of 0 to 2, and the sum of h + i is an integer of 2 to 4. ]
The polylactic acid resin composition according to any one of claims 1 to 3.   The polylactic acid-based resin composition according to any one of claims 1 to 4, wherein the content of the trimesic acid triamide compound is 0.05 to 5 parts by weight with respect to 100 parts by weight of the polylactic acid-based resin.   The resin composition according to any one of claims 1 to 5, wherein the content of the ether ester is 1 to 15 parts by weight with respect to 100 parts by weight of the polylactic acid resin.   The resin composition in any one of Claims 2-6 whose content of a carbodiimide compound is 0.2-5 weight part with respect to 100 weight part of polylactic acid-type resin.   The ratio of the structural unit consisting of L-lactic acid residues to the total structural units constituting the polylactic acid resin is 80 to 99.5 mol%, or the polylactic acid resin constitutes the polylactic acid resin The resin composition in any one of Claims 1-7 whose ratio of the structural unit which consists of D-lactic acid residues with respect to all the structural units to perform is 80-99.5 mol%.   The resin composition in any one of Claims 1-8 whose acid component content is 5 equivalent / tons or less.   The resin composition according to any one of claims 1 to 9, wherein a crystallization completion time is 90 seconds or less.   The molded object formed by shape | molding the resin composition in any one of Claims 1-10.   It is a manufacturing method of the polylactic acid-type resin composition in any one of Claims 1-10, Comprising: (i) (A) Polylactic acid-type resin, (B) Trimesic acid triamide type compound, (C) Ether ester, And (D) a carbodiimide compound used as necessary, or (ii) a method for producing a polylactic acid resin composition, wherein the mixture is melt-kneaded at a temperature higher than the melting temperature of the polylactic acid resin .   The production method according to claim 12, wherein the trimesic acid triamide compound has an average particle size of 10 µm or less and a maximum particle size of 30 µm or less.   A method for producing a molded body from the resin composition according to any one of claims 1 to 10, wherein the resin composition is heated to a temperature equal to or higher than a melting temperature of a trimesic acid triamide compound in a molten polylactic acid resin. Kneaded until the trimesic acid triamide compound is dissolved in the molten polylactic acid resin, and is subjected to a molding step in a state where the trimesic acid triamide compound is dissolved in the molten polylactic acid resin. Method. The method for producing a molded article according to claim 14, wherein the molding step is injection molding, extrusion molding, injection blow molding, injection extrusion blow molding, injection compression molding, extrusion blow molding, extrusion thermoform molding or melt spinning.