JP2010168507A - Polylactic acid composition and molding comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polylactic acid composition that has good hue and excellent hydrolysis-resistant stability and is suitable for industrial production. <P>SOLUTION: The composition contains (i) 100 pts.wt. of polylactic acid (component A) including poly-L-lactic acid and poly-D-lactic acid and having a crystal melting peak of 190&deg;C or higher in the measurement by a differential scanning calorimeter (DSC), (ii) 0.01-5 pts.wt. of an aliphatic amide (component B) of an aliphatic acid having an acid number of less than 10, and (iii) 0.01-5 pts.wt. of a metal salt (component C) of a phosphoric acid ester having an acid number of less than 5, and has the retention of reduced viscosity (&eta;<SP>R</SP>) represented by formula described below of 70% or more. &eta;<SP>R</SP>(%)=&eta;<SP>1</SP>/&eta;<SP>0</SP>(&eta;<SP>0</SP>is initial reduced viscosity, and &eta;<SP>1</SP>is reduced viscosity after held at 80&deg;C with 95% RH atmosphere for 72 hours). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to polylactic acid (component A) containing a stereocomplex phase (hereinafter sometimes referred to as complex phase), an aliphatic amide (component B) of a fatty acid having an acid value of less than 10, and a phosphate ester having an acid value of less than 10. The present invention relates to a composition containing a metal salt (component C), having good hue and heat-and-moisture stability, and suitable for industrial production, and a molded article comprising the same.

In recent years, for the purpose of protecting the global environment, biodegradable polymers that are decomposed in a natural environment have attracted attention and are being studied all over the world. As biodegradable polymers, aliphatic polyesters such as polylactic acid, polyhydroxybutyrate and polycaprolactone are known. Since polylactic acid uses lactic acid obtained from a raw material derived from a living body or a derivative thereof as a raw material, it is a high-safety and environmentally friendly polymer material. Therefore, the use as a general-purpose polymer is examined, and the use as a stretched film, a fiber, an injection molded product, etc. is examined.
However, polylactic acid has a low crystal melting temperature of about 155 ° C., so there is a limit to heat resistance, and since it is easily decomposed by humidity, there is a limit to heat and heat resistance stability. There was a limit to formability as well as use as a molded product.

In order to improve moldability, a method of adding an agent for promoting crystallization such as a crystallization nucleating agent has been proposed (Patent Document 1). It has also been proposed to use a phosphate ester metal salt of a crystallization nucleating agent and a fatty acid amide in combination (Patent Document 2). A method of adding an organic or inorganic filler has been proposed (Patent Document 3). According to these proposals, some improvement has been seen in improving the crystallization speed and heat resistance of homopolymers, random copolymers, block copolymers, and mixtures of L-lactic acid units or D-lactic acid units. However, no studies have been made on polylactic acid containing a complex phase.
That is, poly L-lactic acid (hereinafter sometimes abbreviated as PLLA) composed of L-lactic acid units and poly D-lactic acid (hereinafter sometimes abbreviated as PDLA) composed of D-lactic acid units are in solution or in a molten state. It is known that stereocomplex polylactic acid is formed by mixing in (Patent Document 4 and Non-Patent Document 1). This stereocomplex polylactic acid has a crystal melting temperature of 200 to 230 ° C., a higher melting point than PLLA and PDLA, and an interesting phenomenon showing high crystallinity has been discovered.

However, formation of stereocomplex polylactic acid is not easy, and the difficulty becomes even more pronounced especially when the weight average molecular weight of PLLA or PDLA exceeds 150,000 (Patent Document 4).
That is, a stereocomplex polylactic acid usually does not show a single phase, and is a PLLA and PDLA phase (hereinafter sometimes referred to as a homo phase) and a polylactic acid stereocomplex phase (hereinafter sometimes referred to as a complex phase). It becomes a mixed phase composition. In this mixed composition, if the ratio of the complex phase is small, it is difficult to exhibit the heat resistance inherent in stereocomplex polylactic acid.

In addition, stereocomplex polylactic acid has a higher crystal melting temperature than homophase polylactic acid, so it needs to be processed at a higher temperature than homophase polylactic acid. The solution of this problem is awaited.
In order to improve the heat-and-moisture stability of polylactic acid or stereocomplex polylactic acid, it has been proposed to improve the heat-and-moisture stability by blocking carboxyl groups with a carbodiimide compound (Patent Documents 5 and 6).
However, in these proposals, the carbodiimide compound kneaded in the resin may be thermally decomposed during melt molding to deteriorate the hue of the resin. In addition, since the carbodiimide compound is blended in the resin in a relatively large amount of the order of%, the hue of the molded product may be remarkably deteriorated. For example, according to the above document, the color b * value of the polylactic acid drawn yarn when no carbodiimide is added is 1.7, whereas when the carbodiimide is added, it is extremely deteriorated to about 3.5. According to the knowledge of the inventors, the use as a product is a problem.
It is also clear that carbodiimide compounds are thermally decomposed during melt molding and the molded product is colored, and it also becomes clear that there is a problem of deteriorating the working environment by generating bad odor, and the problem of deteriorating the working environment is urgently solved. .

JP 2003-192894 A JP 2004-224990 A Japanese Patent Laid-Open No. 2005-2174 JP 63-24014 A JP 2004-332166 A JP 2005-350829 A

Macromolecules, 24, 5651 (1991).

  An object of the present invention is to provide a polylactic acid composition which is excellent in hue and heat-and-heat stability and suitable for industrial production. A further object of the present invention is to provide a polylactic acid composition containing stereocomplex polylactic acid and having the above properties and excellent heat resistance.

  The inventors of the present invention have completed the present invention as a result of intensive studies in order to solve the above problems. That is, the present inventors contain polylactic acid (A component) including a stereocomplex phase, an aliphatic amide of a fatty acid having an acid value of less than 10 (B component), and a phosphoric acid ester metal salt (C component) having an acid value of less than 5. This composition is suitable for industrial production, excellent in hue and heat resistance, and found to have a reduced viscosity retention of 70% or more when held at 80 ° C. and 95% RH for 72 hours. Completed the invention.

That is, the present invention
1. (i) 100 parts by weight of polylactic acid (A component) containing poly L-lactic acid and poly D-lactic acid and having a crystal melting peak of 190 ° C. or higher by differential scanning calorimetry (DSC) measurement,
(ii) 0.01 to 5 parts by weight of an aliphatic amide (component B) of a fatty acid having an acid value of less than 10, and
(iii) 0.01 to 5 parts by weight of a phosphoric acid ester metal salt (C component) having an acid value of less than 5, and the following formula η ^R (%) = η ¹ / η ⁰
(Η ⁰ is the initial reduced viscosity, and η ¹ is the reduced viscosity after holding for 72 hours in an atmosphere of 80 ° C. and 95% RH.)
A composition having a reduced viscosity retention (η ^R ) represented by:
2. 2. The composition according to item 1 above, wherein the stereogenicity (S) defined by the following formula (i) is 90 to 100%;
S = [ΔHms / (ΔHmh + ΔHms)] × 100 (i)
(ΔHms = Stereocomplex phase polylactic acid melting enthalpy, ΔHmh = Polylactic acid homophase crystal melting enthalpy)
3. The composition according to item 1 or 2, wherein the aliphatic amide (component B) contains a mixed fatty acid residue having 10 to 30 carbon atoms derived from a living body,
4). The composition according to any one of the preceding items 1 to 3, wherein the phosphoric acid ester metal salt (component C) is represented by the following formula (ii) or (iii):

(In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. M ₁ is an alkali metal. An atom, an alkaline earth metal atom, a zinc atom or an aluminum atom, p is 1 or 2. q is 0 when M ₁ is an alkali metal atom, an alkaline earth metal atom or a zinc atom, and is an aluminum atom. Is 1 or 2.)

Wherein R ₄ and R ₅ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. M ₂ is an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom. 1 or 2 q is 0 when M ₂ is an alkali metal atom, alkaline earth metal atom or zinc atom, and 1 or 2 when M ₂ is an aluminum atom.
5). The composition according to any one of the preceding items 1 to 4, wherein the ratio (B / C) of the number of moles of the amide group of the component B to the number of moles of the phosphorus element of the component C is 50/1 to 1/1.
6). A melt-molded article comprising the composition according to any one of items 1 to 5,
7). The melt-molded product according to the above item 6, which is a film, fiber, fiber structure, or injection-molded product,
It is.

  The composition of the present invention contains a complex phase, has good hue, heat resistance and moist heat resistance, and is suitable for industrial production. The composition of the present invention can be used stably over a long period of time in an atmosphere of high relative humidity.

  Hereinafter, the present invention will be described in detail.

<Fatty acid amide (component B)>
The fatty acid amide (B component) is an amide compound comprising a fatty acid component and an amide-forming aliphatic amino compound. The fatty acid component is made of at least one kind of saturated and / or unsaturated fatty acid having 10 to 30 carbon atoms.
Content of B component in the composition of this invention is 0.01-5 weight part per 100 weight part of A component, Preferably it is 0.02-4 weight part, More preferably, it is 0.05-3 weight part. .
In the composition of the present invention, the ratio (B / C) between the number of moles of the amide group of the component B and the number of moles of the phosphorus element of the component C is preferably 50/1 to 1/1.

Phosphoric acid ester metal salt (component C) is necessary to increase the degree of stereolification (S) of polylactic acid (component A), but may reduce the wet heat resistance of polylactic acid. Therefore, it becomes possible to suitably suppress the undesirable action of the C component by containing an aliphatic amide (B component) of a fatty acid.
Examples of the fatty acid include saturated fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and serotic acid. Δ9-decylenic acid, sterling acid, Δ9-dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, patroceric acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, punicic acid, licanoic acid, parinaric acid, gardole Illustrative examples include unsaturated fatty acids such as acid, arachidonic acid, 5-eicosenoic acid, 5-docosenoic acid, cetreic acid, erucic acid, 5,13-docosadienoic acid, ceracoleic acid, stearoleic acid, and taliphosphoric acid, and mixed fatty acids thereof. The
Examples of the mixed fatty acid include biologically derived fatty acids such as coconut oil, babas oil, palm oil, olive oil, castor oil, peanut oil, rapeseed oil, cow oil, pig oil, and whale oil.
The aliphatic amide (component B) preferably contains a mixed fatty acid residue having 10 to 30 carbon atoms derived from a living body.

Examples of the B component aliphatic amino compound include mono- or higher-valent amine compounds having a primary or secondary amino group having a C 0-30 aliphatic hydrocarbon group that forms an amide bond with a fatty acid. Is done.
Here, the aliphatic amino compound having 0 carbon atoms means ammonia, and the compound having a tertiary amino group is not included in the aliphatic amino compound of the present invention because it has no amide-forming ability.
The aliphatic amide (component B) of the fatty acid referred to in the present invention is a compound comprising the above-mentioned fatty acid and an aliphatic amino compound, saturated fatty acid mono, polyamide, unsaturated fatty acid mono, polyamide, and hydrogen of these amide groups. A compound having a structure substituted with an alkyl group.

Examples of such (component B) include saturated fatty acid amides such as capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, arachidic acid amide, behenic acid amide, lignoceric acid amide, and serotic acid amide. Is mentioned.
Δ9-decylenic acid amide, sterling acid amide, Δ9-dodecylenic acid amide, palmitoleic acid amide, oleic acid amide, ricinoleic acid amide, patroceric acid amide, vaccenic acid amide, linoleic acid amide, linolenic acid amide, eleostearic acid amide , Punicic acid amide, licanoic acid amide, parinaric acid amide, gadoleic acid amide, arachidonic acid amide, 5-eicosenoic acid amide, 5-docosenoic acid amide, cetreic acid amide, erucic acid amide, 5,13-docosadienoic acid amide, ceracolein Examples thereof include unsaturated fatty acid amides such as acid amides, stearolic acid amides, and taliphosphoric acid amides, mixtures thereof, and mixed fatty acid amides.

Furthermore, N-lauryl lauric acid amide, N-palmityl palmitic acid amide, N-stearyl stearic acid amide, N-behenyl behenic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, Examples thereof include amide compounds in which hydrogen of an amide group such as N-stearyl erucamide and N-oleyl palmitate is substituted with an alkyl group.
The alkyl group may have a substituent such as a hydroxyl group introduced into its structure, such as methylol stearamide, methylol behenic acid amide, N-stearyl-1-hydroxystearic acid amide, N-oleyl 1-2-hydroxystearic acid amide and the like are also included in the alkyl-substituted fatty acid monoamide of the present invention.

  Examples of the B component from the polyvalent amino compound include methylene biscaprylic acid amide, methylene biscapric acid amide, methylene bislauric acid amide, methylene bismyristic acid amide, methylene bispalmitic acid amide, methylene bisstearic acid amide, and methylene bis. Isostearic acid amide, methylene bisbehenic acid amide, methylene bisoleic acid amide, methylene biserucic acid amide, ethylene biscaprylic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bismyristic acid amide, ethylene bis Palmitic acid amide, ethylene bis stearic acid amide, ethylene bis isostearic acid amide, ethylene bis behenic acid amide, ethylene bis oleic acid amide, ethylene bis erucic acid amide, Lenbis stearic acid amide, butylene bis behenic acid amide, butylene bis oleic acid amide, butylene biserucic acid amide, hexamethylene bis stearic acid amide, hexamethylene bis behenic acid amide, hexamethylene bis oleic acid amide, hexa Methylene bis erucamide, m-xylylene bis stearamide, m-xylylene bis-1-hydroxy stearamide, p-xylylene bis stearamide, p-phenylene bis stearamide, p-phenylene bis stearin Acid amide, N, N′-distearyl adipic acid amide, N, N′-distearyl sebacic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide, N, N '-Distearyl isophthalate N, N'-distearyl terephthalic acid amide, methylene bishydroxy stearic acid amide, ethylene bis hydroxy stearic acid amide, butylene bis hydroxy stearic acid amide, hexamethylene bis hydroxy stearic acid amide, diethylene triamine tristearyl amide, diethylene triamine trilauryl amide Etc.

Amides of fatty acids having 10 to 30 carbon atoms are preferable because they improve the heat-and-moisture stability more suitably in the composition with polylactic acid (component A) than amides of fatty acids having less than 10 carbon atoms. Furthermore, an amide of a fatty acid having 30 or less carbon atoms is preferably exemplified from the viewpoint of compatibility with polylactic acid.
In terms of compatibility with polylactic acid, the component B preferably contains an unsaturated fatty acid, particularly a mixed fatty acid amide derived from a living body.
That is, the amides of the aforementioned mixed fatty acid derived from a living body are exemplified as a suitable agent having good compatibility in the composition with the component A and excellent in improvement in heat and moisture resistance. Furthermore, fatty acid bisamides and alkyl-substituted fatty acid monoamides are preferably selected from the same viewpoint.

  In the present invention, the fatty acid aliphatic amide (component B) has an acid value of less than 10. This is because when the acid value of the component B exceeds 10, not only the ability to suitably improve the heat and moisture resistance of the composition of the present invention is insufficient, but also the content may be lowered. Fatty acid amides added to polylactic acid as a crystal nucleating agent, lubricant, or lubricant, especially polylactic acid that does not form a complex phase, do not need to be specifically defined for acidic impurity components. There is a need to strictly define the impurities as acid values within the above range.

The acid value of component B is more preferably 0 to less than 5. Setting the acid value to 0 completely is difficult to adopt from the viewpoint of industrial cost, and more preferably the acid value is in the range of less than 0.001 to 1. The acid value of component B is the mg of KOH required for neutralization of 1 g of the agent, dissolved in purified o-cresol under a nitrogen stream, titrated with 0.05 N potassium hydroxide in ethanol using bromocresol blue as an indicator.
The acid value of the B component can be lowered to the above range by dissolving the B component in an ordinarily anhydrous solvent or melting the B component and treating with a strong base compound. Specifically, it can be easily obtained by dissolving B in a low boiling point solvent such as diethyl ether and treating with anhydrous KOH or K ₂ CO ₃ according to a conventional method.
Since the water content of the B component may lower the molecular weight of the polylactic acid component during the production of the composition with polylactic acid (A component), it is preferably used as dry as possible. That is, the water content of the component B is preferably 0 to 1,000 wtppm, more preferably 1 to 300 wtppm, and still more preferably 1 to 100 wtppm.

<Polylactic acid (component A)>
In the present invention, polylactic acid (component A) comprises poly L-lactic acid and poly D-lactic acid, and is a polylactic acid containing a complex phase polylactic acid having a crystal melting peak at 190 ° C. or higher by DSC measurement.
In the present invention, the weight average molecular weight of polylactic acid (component A), and thus poly L-lactic acid and poly D-lactic acid, is preferably selected from the viewpoint of compatibility between moldability and molded article physical properties. If the weight average molecular weight is less than 100,000, the mechanical strength and toughness of the molded product are low, which is not preferable. Further, if the weight average molecular weight exceeds 500,000, the melt viscosity is high, and melt molding becomes difficult. From this viewpoint, the weight average molecular weight is more preferably selected in the range of 110,000 to 350,000, and still more preferably in the range of 1 to 250,000.

Further, in the present invention, poly L-lactic acid and poly D-lactic acid each have a crystal melting peak (Tmh) between 150 and 190 ° C. by differential scanning calorimetry (DSC) measurement, and the heat of crystal melting (ΔHmsc ) Is preferably 10 J / g or more. By satisfying such crystal melting point and crystal melting heat range, the heat resistance of polylactic acid (component A) can be suitably increased.
Furthermore, since the polylactic acid (component A) exhibits the heat resistance inherent in the stereocomplex phase polylactic acid in DSC measurement from the viewpoint of heat resistance, the degree of stereonation (S) defined by the following formula (i) is preferably 90 to 100%, more preferably 95 to 100%. Particularly preferred is when the degree of stereoification is 100%.
S = [ΔHms / (ΔHmh + ΔHms)] × 100 (i)
(However, ΔHms = Crystal melting enthalpy of stereocomplex phase polylactic acid and ΔHmh = Polylactic acid homophase crystal melting enthalpy)
Furthermore, the polylactic acid (component A) containing a complex phase preferably has crystallinity, and is defined by the stereo ratio defined by the following formula (ii) depending on the intensity ratio of diffraction peaks by wide-angle X-ray diffraction (XRD) measurement. The conversion rate (Sc) is more preferably 50% or more.
Sc (%) = [ΣISCi / (ΣISCi + IHM)] × 100 (ii)
[Where ΣISCi = ISC1 + ISC2 + ISC3 and ISCi (i = 1 to 3) are the integrated intensities of diffraction peaks near 2θ = 12.0 °, 20.7 ° and 24.0 °, respectively, and IHM is 2θ = 16.5 °. It represents the integrated intensity IHM of a diffraction peak derived from a homophase crystal appearing in the vicinity. ]
The stereoization rate (Sc) is preferably in the range of 50 to 100%, more preferably 60 to 95%, and particularly preferably 65 to 90%. When polylactic acid (component A) has Sc in the above range, the heat resistance and heat-and-moisture resistance of the molded product can be more suitably satisfied.

Furthermore, from the same viewpoint, the crystallinity of polylactic acid (component A), particularly the crystallinity by XRD measurement, is at least 5%, preferably 5-60%, more preferably 7-50%, and even more preferably 10-45. % Range.
Furthermore, from the same viewpoint, the crystal melting point of the complex phase polylactic acid is 190 to 250 ° C, more preferably 200 to 230 ° C. The crystal melting enthalpy by DSC measurement is 20 J / g or more, preferably 20 to 80 J / g, more preferably 30 to 80 J / g.
If the crystalline melting point of the complex phase polylactic acid is less than 190 ° C., the significance of complex phase formation, and therefore the significance of the present invention, will be small. Further, when the temperature exceeds 250 ° C., it is necessary to mold the molded product of the present invention at a high temperature of 250 ° C. or higher, and it may be difficult to suppress thermal decomposition of the resin. The same argument applies to the value of crystal melting enthalpy.
In order to suitably satisfy the degree of stereolation and preferably the stereoization rate and the various crystallinity parameters described above, the weight ratio of poly D-lactic acid to poly L-lactic acid is 90/10 to 10 in polylactic acid (component A). It is preferably 10/90. More preferably, it is in the range of 80/20 to 20/80, more preferably 30/70 to 70/30, particularly preferably 40/60 to 60/40, and theoretically preferably as close to 1/1 as possible. Selected.

  In the present invention, poly-D-lactic acid consists of a D-lactic acid unit represented by the formula (iv) as a main component, preferably 90-100 mol% D-lactic acid units and 0-10 mol% D-lactic acid. It consists of copolymerized units other than. The poly-L-lactic acid is composed of L-lactic acid units represented by the formula (iv) as a main component, preferably a copolymer other than 90 to 100 mol% L-lactic acid units and 0 to 10 mol% L-lactic acid. Consists of units.

In the above, the D-, L-lactic acid unit, which is the main repeating unit, is more preferably selected in the range of 95 to 100 mol%, more preferably 98 to 100 mol%. The copolymer unit other than the main repeating unit is preferably selected in the range of 0 to 10 mol%, more preferably 0 to 5 mol%, and still more preferably 0 to 2 mol%.
Copolymerized units include units derived from dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones and the like having functional groups capable of forming two or more ester bonds, and various polyesters, various polyethers, various types composed of these various components. Examples are units derived from polycarbonate and the like.

  Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid. Examples of the polyhydric alcohol include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol. Or aromatic polyhydric alcohol etc., such as what added ethylene oxide to bisphenol, etc. are mentioned. Examples of the hydroxycarboxylic acid include glycolic acid and hydroxybutyric acid. Examples of the lactone include glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, and δ-valerolactone.

The weight average molecular weight of the poly L-lactic acid and poly D-lactic acid of the present invention is preferably 100,000 to 500,000, more preferably 110,000 to 350,000, in order to achieve both the mechanical properties and moldability of the molded article of the present invention. More preferably, a range of 1 to 250,000 is selected.
Poly L-lactic acid and poly D-lactic acid can be produced by a conventionally known method. For example, it can be produced by ring-opening polymerization of L- or D-lactide in the presence of a metal-containing catalyst. The low molecular weight polylactic acid containing a metal-containing catalyst is optionally crystallized or without crystallization, under reduced pressure or from normal pressure to increased pressure, in the presence or absence of an inert gas stream. It can also be produced by solid phase polymerization. Furthermore, it can be produced by a direct polymerization method in which lactic acid is subjected to dehydration condensation in the presence or absence of an organic solvent.

The polymerization reaction can be carried out in a conventionally known reaction vessel. For example, in a ring-opening polymerization or direct polymerization method, a vertical reactor or a horizontal reactor equipped with a stirring blade for high viscosity, such as a helical ribbon blade, is used alone, or Can be used in parallel. Moreover, any of a batch type, a continuous type, a semibatch type may be sufficient, and these may be combined.
Alcohol may be used as a polymerization initiator. Such alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid, such as decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, ethylene glycol, trimethylolpropane, pentaerythritol, etc. Can be suitably used.
It can be said that the polylactic acid prepolymer used in the solid-phase polymerization method is preferably crystallized in advance from the viewpoint of preventing resin pellet fusion. The prepolymer is polymerized in a solid state in a fixed vertical or horizontal reaction vessel, or in a reaction vessel (such as a rotary kiln) that rotates itself like a tumbler or kiln, in the temperature range from the glass transition temperature of the prepolymer to less than the melting point. Is done.

Examples of metal catalysts include alkali metals, alkaline earth metals, rare earths, transition metals, aluminum, germanium, tin, antimony, titanium and other fatty acid salts, carbonates, sulfates, phosphates, oxides, hydroxides, Illustrative are halides, alcoholates and the like. Among them, fatty acid salts, carbonates, sulfates, phosphates, oxides, hydroxides containing at least one metal selected from tin, aluminum, zinc, calcium, titanium, germanium, manganese, magnesium and rare earth elements Products, halides, and alcoholates are preferred.
Tin compounds due to low catalytic activity and side reactions, specifically stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, tin myristate, tin octylate Tin-containing compounds such as tin stearate and tetraphenyltin are exemplified as preferred catalysts.
Among these, tin (II) compounds, specifically, diethoxytin, dinonyloxytin, tin (II) myristate, tin (II) octylate, tin (II) stearate, tin (II) chloride and the like are suitable. Illustrated.

The amount of the catalyst used is 0.42 × 10 ^{−4 to} 100 × 10 ⁻⁴ mol per kg of lactide, and further considering the reactivity, color tone and stability of the resulting polylactides, 1.68 × 10 ^{−4 to} 42 0.1 × 10 ⁻⁴ mol, particularly preferably 2.53 × 10 ^{−4 to} 16.8 × 10 ⁻⁴ mol are used.
The metal-containing catalyst used for polylactic acid polymerization is preferably deactivated with a conventionally known deactivator prior to using polylactic acid.

Examples of such a deactivator include an organic ligand consisting of a group of chelate ligands having an imino group and capable of coordinating to a polymerized metal catalyst, dihydridooxoline (I) acid, dihydridotetraoxodilin (II, II ) Acid, hydridotrioxoline (III) acid, dihydridopentaoxodiphosphorus (III) acid, hydridopentaoxodi (II, IV) acid, dodecaoxohexaphosphorus (III) acid, hydridooctaoxotriphosphate (III, IV) , IV) acid, octaoxotriphosphoric acid (IV, III, IV), hydridohexaoxodiphosphoric acid (III, V), hexaoxodiphosphoric acid (IV), decaoxotetralinic acid (IV), hedecaoxotetralinic acid (IV ) acid, Eneaokiso triphosphate (V, IV, IV) acid value 5 or less low oxidation number phosphoric acids such as acid, the formula _xH 2 _O · _yP 2 O ₅ Polyphosphoric acid represented by x, y = 3, 2> x / y> 1, and referred to as diphosphoric acid, triphosphoric acid, tetraphosphoric acid, pentaphosphoric acid or the like based on the degree of condensation, and mixtures thereof , X / y = 1, especially trimetaphosphoric acid, tetrametaphosphoric acid, 1> x / y> 0, ultralin having a network structure with a part of the phosphorus pentoxide structure Acids (sometimes collectively referred to as metaphosphate compounds), and acid salts of these acids, monovalent and polyhydric alcohols, or partial esters, complete esters, phosphono substitutions of polyalkylene glycols Examples include lower aliphatic carboxylic acid derivatives.

From the catalyst deactivation ability, it is represented by the formula xH ₂ O · yP ₂ O ₅ , x / y = 3 orthophosphoric acid, 2> x / y> 1, and based on the degree of condensation, diphosphate, triphosphate, tetra Polyphosphoric acid called phosphoric acid, pentaphosphoric acid and the like and mixtures thereof, metaphosphoric acid represented by x / y = 1, especially trimetaphosphoric acid, tetrametaphosphoric acid, 1> x / y> 0, Ultraphosphoric acid having a network structure with a part of the phosphorus oxide structure (these may be collectively referred to as metaphosphoric acid compounds), and acid salts of these acids, monovalent and polyhydric alcohols Or partial ester phosphorus oxoacids of polyalkylene glycols or acidic esters thereof, phosphono-substituted lower aliphatic carboxylic acid derivatives and the above-mentioned metaphosphoric acid compounds are preferably used.

  The metaphosphoric acid compound used in the present invention is a cyclic metaphosphoric acid in which about 3 to 200 phosphoric acid units are condensed, an ultra-region metaphosphoric acid having a three-dimensional network structure, or an alkali metal salt or an alkaline earth metal salt thereof. Onium salts). Among them, cyclic sodium metaphosphate, ultra-region sodium metaphosphate, phosphono-substituted lower aliphatic carboxylic acid derivative dihexylphosphonoethyl acetate (hereinafter sometimes abbreviated as DHPA) and the like are preferably used.

The polylactic acid (component A) preferably has a lactide content of 1 to 5,000 wtppm. The lactide contained in polylactic acid (component A) deteriorates the resin and deteriorates the color tone at the time of melt processing, and in some cases, it may be disabled as a product.
Poly L-lactic acid and / or poly D-lactic acid immediately after melt ring-opening polymerization usually contains 1 to 5% by weight of lactide, but poly L-lactic acid and / or poly D-lactic acid is In any stage up to the formation of lactic acid (component A), a conventionally known lactide weight loss method, that is, vacuum devolatilization in a single-screw or multi-screw extruder, or high vacuum treatment in a polymerization apparatus alone Alternatively, the lactide can be reduced to a suitable range when combined.

The smaller the lactide content, the better the melt stability and heat-and-moisture resistance of the resin, but there is also the advantage of lowering the resin melt viscosity, making it reasonable and economical to meet the desired purpose. is there. That is, it is reasonable to set it to 1 to 1,000 wtppm at which practical melt stability is achieved. More preferably, a range of 1 to 700 wtppm, more preferably 2 to 500 wtppm, and particularly preferably 5 to 100 wtppm is selected.
The polylactic acid (component A) has a lactide content within such a range, thereby improving the stability of the resin during melt molding of the molded product of the present invention, and the advantage that the molded product can be efficiently manufactured and the moisture resistance of the molded product. Thermal stability and low gas properties can be improved.
The polylactic acid (component A) containing the complex phase polylactic acid is brought into contact with poly L-lactic acid and poly D-lactic acid in a weight ratio of 10/90 to 90/10, preferably by melt contact, More preferably, it can be obtained by melt-kneading contact.

The contact temperature is selected in the range of 220 to 290 ° C., preferably 220 to 280 ° C., more preferably 225 to 275 ° C. from the viewpoint of improving the stability at the time of melting polylactic acid and the degree of stereoification.
The melt kneading method is not particularly limited, but a conventionally known batch type or continuous type melt mixing apparatus is preferably used. For example, melt-stirred tanks, single- and twin-screw extruders, kneaders, non-shaft vertical stirrers (finishers), “Vivorac” manufactured by Sumitomo Heavy Industries, Ltd., N-SCR, manufactured by Mitsubishi Heavy Industries, Ltd. ) Hitachi's eyeglass blades, lattice blades or Kenix type stirrer, or Sulzer type SMLX type static mixer equipped pipe type polymerization equipment can be used, but self-cleaning type polymerization in terms of productivity, quality of polylactic acid, especially color tone. A device such as a non-shaft vertical stirring tank, an N-SCR, a twin-screw extruder, or the like is preferably used.

<Phosphate metal salt>
The polylactic acid (component A) used in the present invention contains a phosphoric acid ester metal salt (component C) having an acid value of less than 5 as a threonization accelerator in order to promote the formation of a complex phase stably and highly. As such agents, compounds represented by the following formulas (ii) and (iii) are preferably selected. Such phosphate metal salts can be used alone or in combination.

(In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. M ₁ is an alkali metal. An atom, an alkaline earth metal atom, a zinc atom or an aluminum atom, p is 1 or 2. q is 0 when M ₁ is an alkali metal atom, an alkaline earth metal atom or a zinc atom, and is an aluminum atom. Is 1 or 2.)

Wherein R ₄ and R ₅ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. M ₂ is an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom. 1 or 2 q is 0 when M ₂ is an alkali metal atom, alkaline earth metal atom or zinc atom, and 1 or 2 when M ₂ is an aluminum atom.
The phosphoric acid ester metal salt (component C) has an acid value of less than 5. Reduction of the acid value can be achieved by dissolving or dispersing the C component in a low-boiling anhydrous solvent and treating with a strongly basic compound. When the acid value of the C component exceeds 2, the wet heat stability of the polylactic acid (component A) may deteriorate significantly beyond the scope of the present invention, so the acid value of the C component is selected within the above range. It is essential to do. The acid value of component C is preferably in the range of 0 to 4, more preferably in the range of 0.01 to 3, and more preferably in the range of 0.1 to 2.

In these phosphoric acid ester metal salts, M ₁ and M ₂ are preferably Na, K, Al, Mg and Ca, and in particular, K, Na, Al, and especially Al can be most suitably used.
Among them, trade names of “ADEKA STAB” NA-10, NA-11, NA-21, NA-30, NA-35, NA-71 and the like manufactured by ADEKA are exemplified as suitable agents.
The content of the phosphoric ester metal salt (component C) is 0.01 to 5 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0 to 100 parts by weight of polylactic acid (component A). 0.02 to 0.3 parts by weight. When the amount is too small, the effect of improving the degree of stereoization is small, and when too large, the complex phase crystal melting point is lowered, which is not preferable.
Furthermore, if desired, a known crystallization nucleating agent described below can be used in combination in order to enhance the action of the phosphoric acid ester metal salt within a range not departing from the gist of the present invention. Of these, calcium silicate, talc, kaolinite, and montmorillonite are preferably selected.
The amount of crystallization nucleating agent used is 0.05 to 5 parts by weight, more preferably 0.06 to 2 parts by weight, still more preferably 0.06 to 1 part by weight, based on 100 parts by weight of polylactic acid (component A). is there.

In the present invention, in the present invention, in order to further increase the degree of stereolization of polylactic acid, [(epoxy group, oxazoline group, oxazine group, isocyanate group, ketene group and carbodiimide group) (hereinafter abbreviated as a specific functional group) It is preferable to add a compound having at least one functional group selected from the group of
The stereogenic auxiliary agent reacts with the molecular terminal of polylactic acid (component A) to partially link the poly L-lactic acid unit and poly D-lactic acid unit to promote stereo complex phase formation. It is the agent that the present inventors speculate that it is made to be.
As the stereogenic assistant, a known agent can be suitably applied as a carboxyl group-capping agent for conventional polyesters described below. Among them, a carbodiimide compound, an oxazoline compound and the like are suitably selected in the present invention because of the effect of promoting the formation of a complex phase and the hue of the composition.
That is, among the stereogenic auxiliaries, an agent containing an oxazine group, an isocyanate group and a carbodiimide group causes deterioration of the working environment due to bad odor due to thermal decomposition of the agent and deterioration of the color tone of polylactic acid (component A) during complex phase formation. Due to the high risk, it is preferable to prepare a separate working environment for use. When using it, it is limited to the case where emphasis is placed on the formation of a complex phase height, and it should be used as little as possible. It is preferable.

In addition, agents having only a ketene group and an epoxy group are less likely to deteriorate the working environment, but it is preferable to avoid the application of these agents because the effect of the hue deterioration of the resin composition is similar to or greater than that of the carbodiimide compound.
The content of the stereogenic assistant is 1 part by weight or less, preferably 0 to 0.5 part by weight, more preferably 0 to 0.3 part by weight, based on 100 parts by weight of polylactic acid (component A). Preferably it is 0-0.1 weight part.

In the present invention, the polylactic acid (component A) has a carboxyl group concentration of 0.01 to 10 (equivalent / 10 ⁶ g), and {hereinafter (equivalent / 10 ⁶ g) may be abbreviated as (eq / ton). . } Is preferred. A range of 0.02 to 5 (eq / ton) is more preferable, and a range of 0.5 to 3 (eq / ton) is more preferably selected. When the carboxyl group concentration is within this range, the polylactic acid (component A) composition of the present invention and the molded product of the present invention comprising the composition can have good heat resistance, hue, and particularly heat and humidity resistance. . In order to reduce the carboxyl group concentration of polylactic acid (component A) to 10 (eq / ton) or less, a conventionally known method for reducing the carboxyl end group concentration in the polyester composition can be suitably applied. For example, it is also possible to esterify or amidate with an alcohol or amine without adding a conventionally known end capping agent or without adding such a terminal capping agent.
As such an end-capping agent, the above-mentioned stereogenic auxiliary having a specific functional group can effectively cleave a carboxyl group.

  As an epoxy compound that can be used as a stereogenic auxiliary having a specific functional group in the present invention, a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, a glycidyl imide compound, a glycidyl amide compound, and an alicyclic epoxy compound are preferable Can be used. By blending such an agent, formation of a complex phase of polylactic acid (component A) can be promoted, and a polylactic acid molded product having excellent mechanical properties, heat resistance, wet heat resistance, durability, moldability, and the like can be obtained. it can.

  As glycidyl ether compounds, stearyl glycidyl ether, phenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylene glycol diglycidyl ether, polytetramethylene glycol Diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and other bisphenols such as bis (4-hydroxyphenyl) methane and bisphenol A diglycidyl ether type obtained by condensation reaction with epichlorohydrin List epoxy resin Bets can be, among others bisphenol A diglycidyl ether type epoxy resin is preferable.

  Glycidyl ester compounds include glycidyl benzoate, glycidyl stearate, glycidyl stearic acid, diglycidyl terephthalate, diglycidyl phthalate, diglycidyl phthalate, diglycidyl adipate, diglycidyl succinate, diglycidyl succinate Examples thereof include ester, dodecanedioic acid diglycidyl ester, pyromellitic acid tetraglycidyl ester, etc. Among them, benzoic acid glycidyl ester and versatic acid glycidyl ester are preferable.

  Examples of the glycidylamine compound include tetraglycidylamine diphenylmethane, triglycidyl-p-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, and triglycidyl isocyanurate.

  As glycidyl imide and glycidyl amide compounds, N-glycidyl phthalimide, N-glycidyl-4,5-dimethyl phthalimide, N-glycidyl-3,6-dimethyl phthalimide, N-glycidyl succinimide, N-glycidyl-1,2,3 , 4-tetrahydrophthalimide, N-glycidyl maleimide, N-glycidyl benzamide, N-glycidyl stearyl amide, etc., among which N-glycidyl phthalimide is preferable.

  Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexyl-3,4-cyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, N-methyl-4,5- Examples thereof include epoxycyclohexane-1,2-dicarboxylic imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide and the like. Furthermore, a polyepoxy compound containing the above compound as a monomer unit, particularly a polyepoxy compound having an epoxy group as a pendant group in a side chain, and the like can be mentioned as suitable agents.

  As other epoxy compounds, epoxy-modified fatty acid glycerides such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized whale oil, phenol novolac type epoxy resins, cresol novolac type epoxy resins and the like can be used.

Examples of oxazoline compounds that can be used as a stereogenic auxiliary having a specific functional group used in the present invention include 2-methoxy-2-oxazoline, 2-butoxy-2-oxazoline, 2-stearyloxy-2-oxazoline, 2 -Cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline, 2-benzyloxy-2-oxazoline, 2-p-phenylphenoxy-2-oxazoline, 2-methyl-2-oxazoline, 2-cyclohexyl-2- Oxazoline, 2-methallyl-2-oxazoline, 2-crotyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-o-ethylphenyl-2-oxazoline, 2-o-propylphenyl-2-oxazoline, 2- p-phenylphenyl-2-oxazoline, 2 2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline) 2,2'-bis (4-butyl-2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2′-p-phenylenebis (4-methyl-2-oxazoline), 2,2′-p-phenylenebis (4,4′-methyl-2-oxazoline), 2,2 '-Ethylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'-ethylenebis (4-methyl- 2-oxazoline), 2,2′-tetramethylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-cyclohexylenebis (2-oxazoline), 2,2′-diphenylenebis (4 -Methyl-2-oxazoline , And the like more specific oxazoline resin of the present invention.
Among the above oxazoline compounds, 2,2′-m-phenylenebis (2-oxazoline), 2,2′-p-phenylenebis (2-oxazoline) and the specific oxazoline resin of the present invention are selected as preferred.

  Examples of oxazine compounds that can be used as a stereogenic auxiliary having a specific functional group in the present invention include 2-methoxy-5,6-dihydro-4H-1,3-oxazine, 2-hexyloxy-5,6. -Dihydro-4H-1,3-oxazine, 2-decyloxy-5,6-dihydro-4H-1,3-oxazine, 2-cyclohexyloxy-5,6-dihydro-4H-1,3-oxazine, 2- Examples include allyloxy-5,6-dihydro-4H-1,3-oxazine, 2-crotyloxy-5,6-dihydro-4H-1,3-oxazine, and the like.

Further, 2,2′-bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-methylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′- Ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-p-phenylene Bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-P, P′-diphenylenebis (5,6-dihydro-4H-1,3-oxazine) and the like can be mentioned.
Furthermore, a polyoxazine compound containing the above-described compound as a monomer unit, particularly a polyoxazine compound having the above functional group as a pendant group in a side chain, and the like can be mentioned as suitable agents.

Examples of isocyanate compounds that can be used in the present invention include aromatic, aliphatic, and alicyclic isocyanate compounds, and mixtures thereof.
Examples of the monoisocyanate compound that can be used as a stereogenic auxiliary having a specific functional group include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate.

As the diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate Isocyanate, (2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate) mixture, cyclohexane-4,4'-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane Examples thereof include diisocyanate, tetramethylxylylene diisocyanate, and 2,6-diisopropylphenyl-1,4-diisocyanate.
Among these isocyanate compounds, aromatic isocyanates such as 4,4′-diphenylmethane diisocyanate and phenyl isocyanate are preferable.
Examples of ketene compounds that can be used as a stereogenic auxiliary having a specific functional group include aromatic, aliphatic, and alicyclic ketene compounds, and mixtures thereof.

Specific examples of the compound include diphenyl ketene, bis (2,6-di-t-butylphenyl) ketene, bis (2,6-di-isopropylphenyl) ketene, dicyclohexyl ketene and the like.
Among these ketene compounds, aromatic ketenes such as diphenyl ketene, bis (2,6-di-t-butylphenyl) ketene, and bis (2,6-di-isopropylphenyl) ketene are preferable.
One or two or more compounds can be appropriately selected and used as the stereogenic aid and the end capping agent. One of preferred embodiments is to promote the formation of a complex phase with a stereogenic aid and to seal a carboxyl group terminal and a part of an acidic low molecular weight compound.
The composition of the present invention includes a thermoplastic resin other than polylactic acid, a stabilizer, a crystallization accelerator, a filler, a release agent, an antistatic agent, a carboxyl group-reactive terminal without departing from the spirit of the present invention. It can contain at least one selected from the group consisting of a sealant, a plasticizer, an impact stabilizer and the like.

<Thermoplastic resin>
If desired, the composition of the present invention may contain a thermoplastic resin other than polylactic acid. Examples of such thermoplastic resins include polyester resins other than polylactic acid resins, polyamide resins, polyacetal resins, polyolefin resins such as polyethylene resins and polypropylene resins, polystyrene resins, acrylic resins, polyurethane resins, chlorinated polyethylene resins, and chlorinated polypropylenes. Resin, aromatic and aliphatic polyketone resin, fluorine resin, polyphenylene sulfide resin, polyether ether ketone resin, polyimide resin, thermoplastic starch resin, AS resin, ABS resin, AES resin, ACS resin, polyvinyl chloride resin, Polyvinylidene chloride resin, vinyl ester resin, MS resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene oxa De resins, poly-4-methylpentene-1, polyetherimide resin, cellulose acetate resin, and thermoplastic resins such as polyvinyl alcohol resins. Among them, polyester resin other than polyacetal resin and polylactic acid resin, for example, selected from polyester resin such as PET (polyethylene terephthalate), PTT (polytrimethylene terephthalate), PBT (polybutylene terephthalate), PEN (polyethylene naphthalate), and polyamide resin. It is preferable to blend at least one kind.

By blending these resins, the surface properties, moldability, mechanical properties, durability, toughness and the like of the molded product made of the composition of the present invention can be made excellent.
The content of the thermoplastic resin is preferably 0.5 to 200 parts by weight, more preferably 1 to 100 parts by weight, still more preferably 3 to 70 parts by weight, and still more preferably 5 to 5 parts by weight per 100 parts by weight of polylactic acid. 50 parts by weight. By blending these resins, a composition and a molded product having excellent characteristics can be obtained.

<Stabilizer>
The composition of the present invention preferably contains a stabilizer. As a stabilizer, what is used for the stabilizer of a normal thermoplastic resin can be used. For example, an antioxidant, a light stabilizer, etc. can be mentioned. By blending these agents, a molded product having excellent mechanical properties, moldability, heat resistance and durability can be obtained.
Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphite compounds, thioether compounds, and the like.

  Examples of hindered phenol compounds include n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl-5 ′). -T-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexanediol- Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) -Propionate], 2,2′-methylene-bis (4-methyl-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl-) -Hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3- t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane and the like.

  As a hindered amine compound, N, N′-bis-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionylhexamethylenediamine, N, N′-tetramethylene-bis [3- (3′-Methyl-5′-t-butyl-4′-hydroxyphenyl) propionyl] diamine, N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionyl ] Hydrazine, N-salicyloyl-N′-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N′-bis [2- {3- (3,5-di) -T-butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide and the like. Preferably, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate] and tetrakis [methylene-3- (3 ′, 5′-di-t-butyl) -4-hydroxyphenyl) propionate] methane and the like.

As the phosphite compound, those in which at least one P—O bond is bonded to an aromatic group are preferable. Specifically, tris (2,6-di-t-butylphenyl) phosphite, tetrakis ( 2,6-di-t-butylphenyl) 4,4′-biphenylene phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, tris (mixed mono and di-nonylphenyl) phosphite, tris (no Butylphenyl) phosphite, 4,4'-isopropylidene-bis (phenyl - dialkyl phosphite), and the like.
Among them, tris (2,6-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl) -4-Methylphenyl) pentaerythritol-diphosphite, tetrakis (2,6-di-t-butylphenyl) 4,4'-biphenylene phosphite and the like can be preferably used.

  Specific examples of thioether compounds include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-lauryl thiopropionate), Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthio) Propionate) and the like.

  Specific examples of the light stabilizer include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds, hindered amine compounds, and the like.

  Examples of the benzophenone compounds include benzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2 ′. -Dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy -2 - carboxy benzophenone, 2-hydroxy-4- (2-hydroxy-3-methyl - acryloxy-isopropoxyphenyl) benzophenone.

  Examples of the benzotriazole compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5- Di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-t-butyl-4′-methyl-2′-hydroxyphenyl) benzotriazole, 2- (3,5- Di-t-amyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-t-butyl-2-hydroxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (Α, α-dimethylbenzyl) phenyl] benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] 2H- benzotriazole, 2- (4'-octoxy-2'-hydroxyphenyl) benzotriazole.

  Examples of the aromatic benzoate compounds include alkylphenyl salicylates such as pt-butylphenyl salicylate and p-octylphenyl salicylate.

  Examples of oxalic acid anilide compounds include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, and 2-ethoxy-3′-. Examples include dodecyl oxalic acid bisanilide.

  Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3'-diphenyl acrylate, 2-ethylhexyl-cyano-3,3'-diphenyl acrylate, and the like.

  Examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6, 6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2, 6,6-tetramethylpiperidine, 4-octadecyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2 , 6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylcarba Yloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6 -Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6 , 6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethylpi-4-peridyl) adipate, bis (2,2,6,6-tetramethylpi-4-peridyl) terephthalate, 1,2-bis (2,2,6,6-tetramethylpi-4-peridylo) Cis) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyl) -Tolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl -4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- “2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid And 1, 2, 2, 6, 6 A condensate of pentamethyl-4-piperidinol with β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] dimethanol, etc. Can be mentioned. In this invention, a stabilizer component may be used by 1 type and may be used in combination of 2 or more type. As the stabilizer component, a hindered phenol compound and / or a benzotriazole compound are preferable. The content of the stabilizer is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, per 100 parts by weight of polylactic acid (component A).

<Crystallization accelerator>
The composition of the present invention can contain an organic or inorganic crystallization accelerator. By containing the crystallization accelerator, the action of the phosphoric acid ester metal salt can be further enhanced, and a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.
That is, by applying a crystallization accelerator, the moldability and crystallinity of polylactic acid (component A) are improved, and a molded product that is sufficiently crystallized even in normal injection molding and has excellent heat resistance and moist heat resistance is obtained. Can do. In addition, the manufacturing time for manufacturing the molded product can be greatly shortened, and the economic effect is great.
As the crystallization nucleating agent used in the present invention, those generally used as crystallization nucleating agents for crystalline resins can be used, and both inorganic crystallization nucleating agents and organic crystallization nucleating agents are used. be able to.

As inorganic crystallization nucleating agents, talc, kaolin, silica, synthetic mica, clay, zeolite, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium carbonate, calcium sulfate, barium sulfate, calcium sulfide, boron nitride , Montmorillonite, neodymium oxide, aluminum oxide, phenylphosphonate metal salt and the like.
These inorganic crystallization nucleating agents are treated with various dispersing aids in order to enhance the dispersibility in the composition and the effect thereof, and are in a highly dispersed state with a primary particle size of about 0.01 to 0.5 μm. Are preferred.

  Organic crystallization nucleating agents include calcium benzoate, sodium benzoate, lithium benzoate, potassium benzoate, magnesium benzoate, barium benzoate, calcium oxalate, disodium terephthalate, dilithium terephthalate, dipotassium terephthalate, Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, barium myristate, sodium octacolate, calcium octacolate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate , Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicy Organic carboxylic acid metal salts such as zinc acid, aluminum dibenzoate, β-naphthoic acid sodium, β-naphthoic acid potassium, sodium cyclohexanecarboxylic acid and the like, and organic sulfonic acid metal salts such as sodium p-toluenesulfonate and sodium sulfoisophthalate. Can be mentioned.

In addition, stearic acid amide, ethylene bislauric acid amide, palmitic acid amide, hydroxy stearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide) and other organic carboxylic acid amides, low density polyethylene, high density polyethylene, polyiso Propylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, high melting point polylactic acid, sodium salt of ethylene-acrylic acid copolymer, sodium of styrene-maleic anhydride copolymer Examples thereof include salts (so-called ionomers), benzylidene sorbitol and derivatives thereof such as dibenzylidene sorbitol.
Among these, at least one selected from talc and organic carboxylic acid metal salts is preferably used. Only one type of crystallization nucleating agent may be used in the present invention, or two or more types may be used in combination.
The content of the crystallization accelerator is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight per 100 parts by weight of polylactic acid.

<Filler>
In the present invention, an organic or inorganic filler can be contained. By containing the filler component, a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.
Organic fillers such as rice husks, wood chips, okara, waste paper ground materials, clothing ground materials, cotton fibers, hemp fibers, bamboo fibers, wood fibers, kenaf fibers, jute fibers, banana fibers, coconut fibers Plant fibers such as pulp, cellulose fibers processed from these plant fibers and fibrous fibers such as animal fibers such as silk, wool, Angola, cashmere, camel, etc., synthetic fibers such as polyester fibers, nylon fibers and acrylic fibers , Paper powder, wood powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch and the like. From the viewpoint of moldability, powdery materials such as paper powder, wood powder, bamboo powder, cellulose powder, kenaf powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein powder, and starch are preferred. Powder, bamboo powder, cellulose powder and kenaf powder are preferred. Paper powder and wood powder are more preferable. Paper dust is particularly preferable.

These organic fillers may be collected directly from natural products, but may be recycled recycled waste paper such as waste paper, waste wood and old clothes.
The wood is preferably a softwood material such as pine, cedar, oak or fir, or a hardwood material such as beech, shii or eucalyptus.
Paper powder is an adhesive from the viewpoint of moldability, especially emulsion-based adhesives such as vinyl acetate resin-based emulsions and acrylic resin-based emulsions when processing paper, polyvinyl alcohol-based adhesives, polyamide-based adhesives, etc. Preferred examples include those containing a hot melt adhesive.

In the present invention, the blending amount of the organic filler is not particularly limited, but from the viewpoint of moldability and heat resistance, it is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight per 100 parts by weight of polylactic acid. Parts, more preferably 10 to 150 parts by weight, particularly preferably 15 to 100 parts by weight. If the blending amount of the organic filler is less than 1 part by weight, the effect of improving the moldability of the composition is small, and if it exceeds 300 parts by weight, uniform dispersion of the filler becomes difficult, or other than moldability and heat resistance In addition, the strength and appearance of the material may decrease, which is not preferable.
The composition of the present invention preferably contains an inorganic filler. A composition excellent in mechanical properties, heat resistance and moldability can be obtained by the inorganic filler. As the inorganic filler used in the present invention, a fibrous, plate-like, or powder-like material used for reinforcing ordinary thermoplastic resins can be used.

  Specifically, for example, carbon nanotube, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, imogolite, sepiolite, Asbestos, slag fiber, zonolite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, and other fibrous inorganic fillers, layered silicate, and organic onium ions Layered silicate, glass flake, non-swelling mica, graphite, metal foil, ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, powdered silicic acid, feldspar powder, potassium titanate, shirasuba Plates and particles of inorganic fillers such as carbon nanoparticles such as carbon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dosonite and white clay fullerene Agents.

Specific examples of layered silicates include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halosite, kanemite, and kenyanite, Li-type fluorine teniolite, Na And swellable mica such as Li-type fluorine teniolite, Li-type tetrasilicon fluorine mica and Na-type tetrasilicon fluorine mica. These may be natural or synthetic. Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Li type fluorine teniolite and Na type tetrasilicon fluorine mica are preferable.
Among these inorganic fillers, fibrous or plate-like inorganic fillers are preferable, and glass fiber, wollastonite, aluminum borate whisker, potassium titanate whisker, mica, and kaolin, a cation-exchanged layered silicate. Is preferred. The aspect ratio of the fibrous filler is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.

Such a filler may be coated or converged with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or may be treated with a coupling agent such as aminosilane or epoxysilane. May be.
The amount of the inorganic filler is preferably 0.1 to 200 parts by weight, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 50 parts by weight, particularly preferably 1 to 100 parts by weight of polylactic acid. -30 parts by weight, most preferably 1-20 parts by weight.

<Release agent>
In the composition of the present invention, a release agent is preferably blended. As the mold release agent used in the present invention, those used for ordinary thermoplastic resins can be used.
Specific examples of release agents include fatty acids, fatty acid metal salts, oxy fatty acids, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid partial saponified esters, fatty acid lower alcohol esters, fatty acid polyvalents. Examples include alcohol esters, fatty acid polyglycol esters, and modified silicones. By blending these, a polylactic acid molded product excellent in mechanical properties, moldability, and heat resistance can be obtained.
Fatty acids having 6 to 40 carbon atoms are preferred. Specifically, oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, montan Examples thereof include acids and mixtures thereof. The fatty acid metal salt is preferably an alkali (earth) metal salt of a fatty acid having 6 to 40 carbon atoms, and specific examples include calcium stearate, sodium montanate, calcium montanate, and the like.

Examples of the oxy fatty acid include 1,2-oxysteric acid. Paraffin having 18 or more carbon atoms is preferable, and examples thereof include liquid paraffin, natural paraffin, microcrystalline wax, petrolactam and the like.
As the low molecular weight polyolefin, for example, those having a molecular weight of 5,000 or less are preferable, and specific examples include polyethylene wax, maleic acid-modified polyethylene wax, oxidized type polyethylene wax, chlorinated polyethylene wax, and polypropylene wax. Fatty acid amides having 6 or more carbon atoms are preferred, and specific examples include oleic acid amide, erucic acid amide, and behenic acid amide.
The alkylene bis fatty acid amide is preferably one having 6 or more carbon atoms, and specifically includes methylene bis stearic acid amide, ethylene bis stearic acid amide, N, N-bis (2-hydroxyethyl) stearic acid amide and the like. As the aliphatic ketone, those having 6 or more carbon atoms are preferable, and examples thereof include higher aliphatic ketones.

Examples of the fatty acid partial saponified ester include a montanic acid partial saponified ester. Examples of the fatty acid lower alcohol ester include stearic acid ester, oleic acid ester, linoleic acid ester, linolenic acid ester, adipic acid ester, behenic acid ester, arachidonic acid ester, montanic acid ester, isostearic acid ester and the like.
Examples of fatty acid polyhydric alcohol esters include glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimyristate, pentaerythritol Examples include tall stearate, pentaerythritol adipate stearate, and sorbitan monobehenate. Examples of fatty acid polyglycol esters include polyethylene glycol fatty acid esters and polypropylene glycol fatty acid esters.

Examples of the modified silicone include polyether-modified silicone, higher fatty acid alkoxy-modified silicone, higher fatty acid-containing silicone, higher fatty acid ester-modified silicone, methacryl-modified silicone, and fluorine-modified silicone.
Of these, fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, fatty acid partial saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, and alkylene bis fatty acid amide are preferred, and fatty acid partial saponified ester and alkylene bis fatty acid amide are more preferred. Of these, montanic acid ester, montanic acid partial saponified ester, polyethylene wax, acid value polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylene bisstearic acid amide are preferred, and particularly, montanic acid partial saponified ester and ethylene bisstearic acid amide are preferred. preferable.
A mold release agent may be used by 1 type and may be used in combination of 2 or more type. The content of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight with respect to 100 parts by weight of polylactic acid.

<Antistatic agent>
Examples of the antistatic agent used in the present invention include (β-lauramidopropionyl) trimethylammonium sulfate, quaternary ammonium salt compounds such as sodium dodecylbenzenesulfonate, sulfonate compounds, alkyl phosphate compounds, and the like. It is done.
In the present invention, the antistatic agent may be used alone or in combination of two or more. The content of the antistatic agent is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of polylactic acid.

<Plasticizer>
As the plasticizer used in the present invention, generally known plasticizers can be used. Examples include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, phosphate ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers.

As a polyester plasticizer, acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, Examples thereof include polyesters composed of diol components such as 1,6-hexanediol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or a monofunctional alcohol.
Examples of the glycerol plasticizer include glycerol monostearate, glycerol distearate, glycerol monoacetomonolaurate, glycerol monoacetomonostearate, glycerol diacetomonooleate, and glycerol monoacetomonomontanate.

Polyvalent carboxylic acid plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, trimellitic acid tributyl, trimellitic acid trioctyl, Trimellitic acid esters such as trihexyl meritate, isodecyl adipate, adipic acid esters such as adipate-n-decyl-n-octyl, citrate esters such as tributyl acetylcitrate, and bis (2-ethylhexyl) azelate Examples include sebacic acid esters such as azelaic acid ester, dibutyl sebacate, and bis (2-ethylhexyl) sebacate.
Examples of the phosphate ester plasticizer include tributyl phosphate, tris phosphate (2-ethylhexyl), trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl-2-ethylhexyl phosphate, and the like.

Polyalkylene glycol plasticizers such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (ethylene oxide.propylene oxide) block and / or random copolymers, ethylene oxide addition polymers of bisphenols, tetrahydrofuran addition polymers of bisphenols, etc. And end-capping compounds such as a terminal epoxy-modified compound, a terminal ester-modified compound, and a terminal ether-modified compound.
Examples of the epoxy plasticizer include an epoxy triglyceride composed of alkyl epoxy stearate and soybean oil, and an epoxy resin using bisphenol A and epichlorohydrin as raw materials.

Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol-bis (2-ethylbutyrate), and fatty acids such as stearamide. Examples thereof include fatty acid esters such as amide and butyl oleate, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils, and paraffins.
As the plasticizer, at least one selected from polyester-type plasticizers and polyalkylene-type plasticizers can be preferably used, and only one type may be used, or two or more types may be used in combination.
The content of the plasticizer is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight, and still more preferably 0.1 to 10 parts by weight per 100 parts by weight of polylactic acid. In the present invention, each of the crystallization nucleating agent and the plasticizer may be used alone, or more preferably used in combination.

<Impact resistance improver>
The impact resistance improver used in the present invention can be used to improve the impact resistance of thermoplastic resins, and is not particularly limited. For example, at least one selected from the following impact resistance improvers can be used.

  Specific examples of impact modifiers include ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1 copolymers, various acrylic rubbers, ethylene-acrylic acid copolymers and their Alkali metal salt (so-called ionomer) ethylene-glycidyl (meth) acrylate copolymer, ethylene-acrylate copolymer (for example, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer), modified ethylene- Propylene copolymer, diene rubber (eg, polybutadiene, polyisoprene, polychloroprene), diene and vinyl copolymer (eg, styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer) , Styrene-a A random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene grafted with styrene, butadiene-acrylonitrile copolymer), polyisobutylene, isobutylene and butadiene or Examples include copolymers with isoprene, natural rubber, thiocol rubber, polysulfide rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber, and the like.

In addition, those having various cross-linking degrees, various micro structures such as those having a cis structure, a trans structure, etc., a core layer and one or more shell layers covering the core layer, and adjacent layers are composed of heterogeneous polymers. A so-called core-shell type multi-layered polymer can also be used.
Furthermore, the various (co) polymers mentioned in the above specific examples may be any of random copolymers, block copolymers, block copolymers and the like, and can be used as the impact resistance improver of the present invention.
The impact resistance improver is preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, and still more preferably 10 to 20 parts by weight with respect to 100 parts by weight of polylactic acid.

<Others>
Moreover, in this invention, you may contain thermosetting resins, such as a phenol resin, a melamine resin, a thermosetting polyester resin, a silicone resin, an epoxy resin, in the range which is not contrary to the meaning of this invention. In the present invention, flame retardants such as bromine, phosphorus, silicone, and antimony compounds may be included within the scope not departing from the spirit of the present invention. Colorants containing organic and inorganic dyes and pigments, for example, oxides such as titanium dioxide, hydroxides such as alumina white, sulfides such as zinc sulfide, ferrocyanides such as bitumen, and chromium such as zinc chromate Contains acid salts, sulfates such as barium sulfate, carbonates such as calcium carbonate, silicates such as ultramarine, phosphates such as manganese violet, carbon such as carbon black, metal colorants such as bronze powder and aluminum powder, etc. You may let them. Also, nitroso type such as naphthol green B, nitro type such as naphthol yellow S, azo type such as naphthol red, chromophthal yellow, phthalocyanine type such as phthalocyanine blue and fast sky blue, and condensed polycyclic colorants such as indanthrone blue In addition, additives such as slidability improvers such as graphite and fluorine resin may be added. These additives can be used alone or in combination of two or more.

  A composition containing these additives can be prepared by mixing the respective components. For the mixing, a tumbler, a V-type blender, a super mixer, a nauter mixer, a Banbury mixer, a kneading roll, a monoaxial or biaxial extruder can be used. The resulting composition can be molded as it is or after being once pelletized with a melt extruder.

The composition of the present invention may be in the form of pellets. The melt molding method of the pellet is not limited at all, and a pellet manufactured by a known pellet manufacturing method can be suitably used. That is, the polylactic acid (component A) composition laid out in the form of a strand or plate is in the air after the resin is completely solidified or not completely solidified and still in a molten state, or Methods such as cutting in water are conventionally known, but any of them can be suitably applied in the present invention.
The shape of the pellet may be any shape such as a spherical shape, a die shape, a linear shape, a curved shape, and a cross-sectional shape such as a circle, an ellipse, a flat shape, a triangle, a polygon having a square shape or more, and a star shape. However, it is preferable to have a shape suitable for further molding the pellets by various molding methods. Specifically, the pellet length is preferably 1 to 7 mm, the major axis is 3 to 5 mm, and the minor axis is 1 to 4 mm. Further, it is preferable that the shape does not vary.
The reduced viscosity retention ratio (η ^R ) of the composition of the present invention is 70% or more, preferably 80% or more, more preferably 85% or more.

<Molded product>
The melt-molded product comprising the composition of the present invention is an injection-molded product, an extrusion-molded product, a vacuum, a pressure-molded product, a blow-molded product, etc., specifically, a composite with pellets, fibers and cloth, and other materials. It includes compression molded products such as fiber structures, films, sheets, and sheet nonwoven fabrics. The melt-molded product is preferably a film, fiber, fiber structure or injection-molded product.
Conventionally known molding methods can be applied to the injection molded product of the present invention without any limitation. From the viewpoint of increasing the crystallization of the molded product and the molding cycle during injection molding, the mold temperature is preferably 30 ° C. or more, more preferably Is 60 ° C. or higher, more preferably 70 ° C. or higher. However, in order to prevent deformation of the molded product, the mold temperature is preferably 140 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower.
In addition, these molded products include various housings, gears, gears, etc. Electronic parts, building members, civil engineering members, agricultural materials, automobile parts (interior and exterior parts, etc.), daily parts and the like can be mentioned.

<Fiber and fiber structure>
For the polylactic acid fiber and fiber structure of the present invention, materials obtained by ordinary melt spinning and subsequent post-processing steps can be preferably used.
That is, polylactic acid (component A) is melted by an extruder-type or pressure melter-type melt extruder, measured by a gear pump, filtered in a pack, and then monofilament, multifilament from a nozzle provided on the base. Etc.
The shape of the base and the number of the bases are not particularly limited, and any of circular, irregular, solid, hollow and the like can be adopted. The discharged yarn is immediately cooled and solidified, then converged, added with oil, and wound. The winding speed is not particularly limited, but is preferably in the range of 300 m / min to 5,000 m / min because a stereocomplex crystal is easily formed.

Further, from the viewpoint of stretchability, a winding speed at which the stereo ratio of the undrawn yarn is 0% is preferable. The undrawn yarn that has been wound is then subjected to a drawing step, but the spinning step and the drawing step do not necessarily need to be separated, and even if a direct spinning drawing method is used in which the drawing is continued without being wound once after spinning. I do not care.
The stretching may be one-stage stretching or multi-stage stretching of two or more stages. From the viewpoint of producing a high-strength fiber, the stretching ratio is preferably 3 times or more, and more preferably 4 times or more. Preferably 3 to 10 times is selected. However, if the draw ratio is too high, the fiber is devitrified and whitened, the strength of the fiber is lowered, the elongation at break is too low, and it is not preferable for fiber use.
As a preheating method for stretching, in addition to the temperature rise of the roll, a flat or pin-like contact heater, a non-contact hot plate, a heat medium bath, and the like can be used, and a commonly used method may be used.
Following the stretching, it is preferable that the heat treatment is performed at a temperature of 170 ° C. or higher and lower than the melting point of polylactic acid (component A) before winding. In addition to the hot roller, any method such as a contact heater or a non-contact hot plate can be adopted for the heat treatment. The stretching temperature is selected from the polylactic acid glass temperature to 170 ° C., preferably 70 to 140 ° C., particularly preferably 80 to 130 ° C. After stretching, it is heat-set at 170-220 ° C. under tension to obtain a polylactic acid fiber having a high stereo ratio and low heat shrinkage and a strength of 3.5 cN / dTex or more.

The high-strength, heat-resistant and heat-and-moisture-resistant stability of the present invention can take the form of various fiber structures such as fiber knitted fabrics, nonwoven fabrics, and molded articles such as cups.
Specifically, thread form products such as sewing thread, embroidery thread, string, fabric such as woven fabric, knitting, nonwoven fabric, felt, outer clothes such as shirt, blouson, pants, coat, sweater, uniform, underwear, pantyhose, socks, Lining, interlining, sports clothing, high value-added clothing products such as women's clothing and formal wear, clothing products such as cups and pads, curtains, carpets, chair upholstery, mats, furniture, baskets, furniture upholstery, wall materials, etc. Products for daily use such as belts and slings, as well as various textile products such as canvas, belts, nets, ropes, heavy cloth, bags, industrial materials such as felts and filters, vehicle interior products, and artificial leather products.

The fiber and fiber structure of the present invention may be used alone with polylactic acid (component A) fiber, or may be mixed with other types of fibers. In addition to various combinations with fiber structures composed of other types of fibers, mixed modes include mixed yarns with other fibers, composite false twisted yarns, mixed spun yarns, long and short composite yarns, fluid processed yarns, covering yarns, and twisted yarns. Examples thereof include union, union, pile, pile, mixed cotton, mixed non-woven fabric of long fibers and short fibers, and felt. When mixed, the mixing ratio is selected to be 1% by weight or more, more preferably 10% by weight or more, and further preferably 30% by weight or more in order to exhibit the characteristics of polylactic acid (component A).
Examples of other fibers to be mixed include cellulose fibers such as cotton, hemp, rayon, and tencel, wool, silk, acetate, polyester, nylon, acrylic, vinylon, polyolefin, and polyurethane.

<Film, sheet>
The film and sheet of the present invention are formed by a conventionally known method. For example, in a film or sheet, a molding technique such as extrusion molding or cast molding can be used. That is, an unstretched film is extruded using an extruder or the like equipped with a T die, a circular die or the like, and further stretched and heat-treated to form.
At this time, the unstretched film can be used as it is as a sheet.
When forming into a film, if a material obtained by melt-kneading polylactic acid (component A) and the above-described various components in advance can be used, it can be formed through melt-kneading during extrusion molding. When extruding an unstretched film, an unstretched film with few surface defects can be obtained by blending a molten resin with an electrostatic adhesive such as a sulfonic acid quaternary phosphonium salt.

Moreover, an unstretched film can also be cast-molded by melt | dissolving, casting, and drying-solidifying polylactic acid (A component) and an additive component using solvents, such as chloroform and a methylene dichloride, for example.
Unstretched film can be uniaxially stretched longitudinally in the direction of mechanical flow and transversely uniaxially stretched in the direction perpendicular to the direction of mechanical flow. Simultaneous biaxial stretching by roll and tenter stretching, and simultaneous biaxial stretching by tenter stretching A biaxially stretched film can be produced by stretching by a biaxial stretching method using a method such as tubular stretching. Further, the film is usually subjected to a heat setting treatment after stretching in order to suppress heat shrinkability and the like. The stretched film thus obtained can be subjected to surface activation treatment such as plasma treatment, amine treatment, and corona treatment by a conventionally known method if desired.

  The film and sheet of the present invention can be used in combination with other types of films and sheets other than a single form. Examples of mixed use include various combinations with films and sheets made of other types of materials, such as lamination and lamination, and combinations with other types of forms such as injection molded articles and fiber structures.

Next, the present invention will be described by way of examples. First, the evaluation methods used in the present invention and examples will be described.

(I) Evaluation.
(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer:
The weight average molecular weight and number average molecular weight of the polymer were measured by gel permeation chromatography (GPC) and converted to standard polystyrene.
GPC measurement equipment
Detector: Differential refractometer RID-6A manufactured by Shimadzu Corporation
Column: SHODEX connected in series was used.
Chloroform was used as an eluent, 10 μl of a sample having a concentration of 1 mg / ml (chloroform containing 1% hexafluoroisopropanol) was injected at a temperature of 40 ° C. and a flow rate of 1.0 ml / min.

(2) Lactide content sample was dissolved in chloroform / hexafluoroisopropanol and quantified by ¹ H-NMR method.

(3) Content of specific functional group-containing compound The content was measured by comparing the characteristic absorption of the polylactic acid with the specific functional group using a Magna-750 Fourier transform infrared spectrophotometer manufactured by Thermo Nicolet.

(4) Carboxyl group concentration, acid value The sample was dissolved in purified o-cresol under a nitrogen stream, and titrated with an ethanol solution of 0.05 N potassium hydroxide using bromocresol blue as an indicator.

(5) DSC measurements such as stereogenicity [S (%)] and crystal melting temperature:
The sample was heated up to 250 ° C. at 10 ° C./min under a nitrogen stream in a first cycle using DSC (TA-2920 manufactured by TA Instrument Co., Ltd.), glass transition temperature (Tg), complex phase polylactic acid crystal Melting temperature (Tm *) and complex phase polylactic acid crystal melting enthalpy (ΔHms) and homophase polylactic acid crystal melting enthalpy (ΔHmh) were measured.
In addition, the crystallization start temperature (Tc *) and the crystallization temperature (Tc) were measured by rapidly cooling the measurement sample and then performing a second cycle measurement under the same conditions.
The degree of stereogenicity is a value determined by the following formula (i) from the complex phase and homophase polylactic acid crystal melting enthalpies determined in the above measurement.
S = [ΔHms / (ΔHmh + ΔHms)] × 100 (i)
(However, ΔHms is the melting enthalpy of complex phase crystals, and ΔHmh is the melting enthalpy of homophase polylactic acid crystals.)

(6) Stereo ratio [Sc (%)]
Derived from a complex phase crystal that appears in the vicinity of 2θ = 12.0 °, 20.7 °, 24.0 ° with the ROTA FLEX RU200B type X-ray diffractometer manufactured by Rigaku Co., Ltd. The following formula (ii) stereoization rate (Sc rate) was determined from the sum ΣISCi of the integrated intensities of diffraction peaks and the integrated intensity IHM of diffraction peaks derived from homophase crystals appearing in the vicinity of 2θ = 16.5 °.
Measurement conditions X-ray source Cu-Kα ray (confocal mirror)
Output 45kV x 70mA
Slit 1mmΦ-0.8mmΦ
Camera length 120mm
Integration time 10 minutes Sc (%) = [ΣISCi / (ΣISCi + IHM)] × 100 (ii)

(7) Film thickness (μm)
Micrometer manufactured by Anritsu Co., Ltd .; a film was placed on a K-402B sample stage, and a stylus was pressed, and thickness (μm) data was obtained using an indicator manufactured by the company; KG3001.

(9) Moist heat resistance (%)
The sample was held at 80 ° C. and 95% RH for 72 hours in a pressure cooker, and the retention rate (%) of the reduced viscosity (η _sp / c) was measured and used as a parameter for heat and humidity resistance. When the parameter was 70% or more, the polylactic acid resin composition could be stably used under normal wet heat conditions, and was judged to have passed the durability. The hydrolysis resistance stability is judged to be acceptable when it is less than 70 to 90%, excellent when it is less than 90 to 95%, and particularly excellent when it is 95 to 100%.
The reduced viscosity (η _sp / c) was measured by dissolving 1.2 mg of a sample in 100 ml of [tetrachloroethane / phenol = (6/4) wt mixed solvent] and using an Ubbelohde viscosity tube at 35 ° C. .

(10) Hue As for the hue of the sample, the color b * value was measured with a Z-1001DP color difference meter manufactured by Nippon Denshoku Industries Co., Ltd.

[Production Example 1-1] (Production of poly L-lactic acid: PLLA1)
To 100 parts by weight of L-lactide (manufactured by Musashino Chemical Laboratory Co., Ltd., optical purity 100%), 0.005 part by weight of tin octylate was added, and the reactor was stirred at 180 ° C. in a nitrogen atmosphere with a stirring blade. For 2 hours, adding 1.2 equivalents of phosphoric acid as a catalyst deactivator for tin octylate, and then removing the remaining lactide at 13.3 Pa to obtain chips to obtain poly L-lactic acid. It was.
The obtained L-lactic acid had a weight average molecular weight of 152,000, a glass transition point (Tg) of 55 ° C., a melting point of 175 ° C., a carboxyl group content of 14 eq / ton, and a lactide content of 350 wtppm.

[Production Example 1-2] (Production of poly-D-lactic acid: PDLA1)
The L-lactide of Production Example 1-1 was changed to D-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%), and polymerization was performed under the same conditions to obtain poly-D-lactic acid. The resulting poly-D-lactic acid had a weight average molecular weight of 151,000, a glass transition point (Tg) of 55 ° C., a melting point of 175 ° C., a carboxyl group content of 15 eq / ton, and a lactide content of 450 wtppm. The results are summarized in Table 1.

[Examples 1 to 3]
After mixing 50 parts by weight of each of poly L-lactic acid and poly D-lactic acid obtained in Production Examples 1-1 and 1-2 and a stereogenic accelerator with the composition in Table 2, drying at 110 ° C. for 5 hours The fatty acid amide is supplied from the second supply port from the first supply port of the biaxial kneading apparatus, melt-kneaded while evacuating at a cylinder temperature of 230 ° C. and a vent pressure of 13.3 Pa, and the strand is extruded into the water tank, Chips were formed with a chip cutter to obtain polylactic acid (component A) resins; A1 to A3. The color b * values are summarized in Table 2 as the heat-and-moisture stability and pellet color of the obtained resin.
As the fatty acid amide and phosphate metal salt used in the examples, an agent purified with potassium carbonate dispersed in ether was used. The color b * values are summarized in Table 2 as the heat-and-moisture stability and pellet color of the obtained resin.
Here, the acid values of the fatty acid amide and the phosphoric acid ester metal salt were each 1 or less and the average particle size was 3 μm, and the working environment was determined by the operator's sensory test for the strength of bad odor at the ruder extrusion port.
Working environment: ○ has almost no foul odor. X means strong odor and problem in workability.
In each Example, the lactide content was 50 to 60 ppm, and the carboxyl group concentration was 10 eq / ton or less, which was a satisfactory level.

[Comparative Examples 1-4]
Polylactic acid (CA4 to CA6) having the composition shown in Table 2 was prepared in the same manner as in Example 1, except that the carbodiimide compound was supplied from the second supply port to produce a composition. The results are summarized in Table 2.
In each comparative example, the lactide content is a good level of 50 to 60 ppm, but in Comparative Examples 1 and 2, the working environment and moisture heat stability are both poor, and in Comparative Example 3 carbodiimide is not used, so the working environment is Although it was in good condition, the stability against wet heat was unsatisfactory. In addition, when fatty acid amides and phosphate ester salts having a high acid value are used, the working environment is acceptable, but it is easily understood that the wet heat stability is poor.

[Example 4]
The polylactic acid (A2) of Example 2 was melted at 240 ° C. using a melt spinning machine with a single-screw rudder and discharged from a die having 36 holes of 0.25Φ at 40 g / min. The temperature under the pack immediately after discharge was 180 ° C., cooled by a spinning cylinder, converged, added with an oil agent, and wound an undrawn yarn at a speed of 500 m / min. This undrawn yarn having a Sc conversion rate of 0% and a stereolation degree of 95% was drawn 4.9 times at 90 ° C. preheating and subsequently heat-set at 140 ° C. to obtain 160 dtex / 36 fil polylactic acid fibers. The fiber was successfully spun, drawn and heat-set without any problems.
The obtained drawn yarn showed a single melting peak of a stereocomplex crystal composed of poly-L-lactic acid and poly-D-lactic acid in a differential scanning calorimeter (DSC) measurement, and had a melting point of 223 ° C. In addition, the Sc conversion ratio in wide-angle X-ray diffraction measurement is 45%, the strength of the fiber is 4.1 cN / dtex, the elongation is 35%, and the fiber color b * value is 1.2. Was.

[Comparative Example 4]
The polylactic acid (CA2) of Comparative Example 2 was obtained in the same manner as in Example 7 using a melt spinning machine with a single-screw rudder to obtain 160 dtex / 36 fil polylactic acid fibers. The obtained drawn yarn showed a single melting peak of a stereocomplex crystal composed of poly L-lactic acid and poly D-lactic acid in a differential scanning calorimeter (DSC) measurement, and the melting point was 222 ° C. In addition, the Sc conversion rate in wide-angle X-ray diffraction measurement was 45%, the strength of the fiber was 4.6 cN / dtex, and the elongation was 35%. .8, and a bad odor around the spinning device, indicating that there is a problem in production.

[Example 5]
After mixing 0.5 parts by weight of tetrabutylphosphonium 3,5-dicarboxybenzenesulfonate with a Henschel mixer per 100 parts by weight of the polylactic acid (A2) of Example 2, it was dried at 110 ° C. for 5 hours, and then biaxial extrusion The mixture was melt kneaded at a cylinder temperature of 230 ° C. in a machine, melt-extruded into a film at a die temperature of 220 ° C., and adhered and solidified to the mirror-cooled drum surface by an electrostatic casting method using a platinum-coated linear electrode.
The unstretched film was stretched at a stretching temperature of 100 ° C., stretched 2.0 times in the longitudinal direction, 2.3 times in the transverse direction, and further heat-set at 145 ° C. to obtain a biaxially stretched film having a thickness of about 50 μm. These films were successfully formed, stretched and heat-set without problems.
Breaking strength of the obtained film (MD / TD is 59/59 MPa, breaking elongation (MD / TD) is 81/73%, all light transmittance is 90% or more, and further after heat treatment at 90 ° C. for 5 hours. Was also good at 90% or more.

[Comparative Example 5]
When the polylactic acid (CA2) of Comparative Example 2 was used to form a film in the same manner as in Example 5, it was judged that there was a problem in industrial production because of the strong odor around the die.

Claims (7)

(i) 100 parts by weight of polylactic acid (A component) containing poly L-lactic acid and poly D-lactic acid and having a crystal melting peak of 190 ° C. or higher by differential scanning calorimetry (DSC) measurement,
(ii) 0.01 to 5 parts by weight of an aliphatic amide (component B) of a fatty acid having an acid value of less than 10, and
(iii) 0.01 to 5 parts by weight of a phosphoric acid ester metal salt (component C) having an acid value of less than 5,
A composition having a reduced viscosity retention rate (η ^R ) represented by the following formula of 70% or more.
η ^R (%) = η ¹ / η ⁰
(Η ⁰ is the initial reduced viscosity, and η ¹ is the reduced viscosity after holding for 72 hours in an atmosphere of 80 ° C. and 95% RH.) The composition according to claim 1, wherein the stereogenicity (S) defined by the following formula (i) is 90 to 100%.
S = [ΔHms / (ΔHmh + ΔHms)] × 100 (i)
(ΔHms = Stereocomplex phase polylactic acid melting enthalpy, ΔHmh = Polylactic acid homophase crystal melting enthalpy) The composition according to claim 1 or 2, wherein the aliphatic amide (component B) contains a mixed fatty acid residue having 10 to 30 carbon atoms derived from a living body. The composition according to any one of claims 1 to 3, wherein the phosphoric acid ester metal salt (component C) is represented by the following formula (ii) or (iii).

(In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. M ₁ is an alkali metal. An atom, an alkaline earth metal atom, a zinc atom or an aluminum atom, p is 1 or 2. q is 0 when M ₁ is an alkali metal atom, an alkaline earth metal atom or a zinc atom, and is an aluminum atom. Is 1 or 2.)

Wherein R ₄ and R ₅ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. M ₂ is an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom. 1 or 2 q is 0 when M ₂ is an alkali metal atom, alkaline earth metal atom or zinc atom, and 1 or 2 when M ₂ is an aluminum atom. The composition according to any one of claims 1 to 4, wherein the ratio (B / C) of the number of moles of the amide group of the component B to the number of moles of the phosphorus element of the component C is 50/1 to 1/1. . A melt-formed product comprising the composition according to any one of claims 1 to 5. The melt molded article according to claim 6, which is a film, a fiber, a fiber structure, or an injection molded article.