JPH1087975A - Polylactic acid-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polylactic acid-based resin composition useful as an environment protecting material, etc., excellent in crystallizability, mold release characteristics and biodegradability, capable of shortening the molding cycle, by blending a polylactic acid-based resin with a specific amide-based compound in a prescribed ratio. SOLUTION: This composition is obtained by blending (A) 100 pts.wt. of a polylactic acid-based resin such as poly L-lactide with (B) 0.01-5 pts.wt. of one or more amide-based compounds of formula I [R<1> is a 2-30C (un)saturated aliphatic polycarboxylic acid residue, an (un)saturated alicyclic polycarboxylic acid residue or an aromatic polycarboxylic acid residue; R<2> is a 1-18C alkyl, a 2-18C alkenyl, phenyl, etc.; (a) is 2-6] or formula II [R<9> is a 3-25C (un)saturated alicuyclic polyamine residue or aromatic polyamine resin; R<10> is R<2> ; (f) is (a)] such as trimesic acid (t-butylamide).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polylactic acid resin composition. More specifically, a polylactic acid-based resin composition having a high crystallization rate, excellent moldability and releasability, and useful as a material for, for example, injection molding, extrusion molding, blow molding, vacuum molding, melt spinning, and stretching. About.

[0002]

2. Description of the Related Art Recently, polylactic acid has attracted attention as a biodegradable polymer that decomposes in a natural environment. In particular, since it will eventually be incorporated into the natural material cycle as carbon dioxide and water, its uses are:
In addition to conventional medical materials, recently, application development to general-purpose materials that are expected to be disposed of into the environment after use has been studied.

[0003] In particular, in addition to its excellent biodegradation properties and transparency, and good compatibility with other polymers and easy modification, it can be easily decomposed into monomers by a heating operation or addition of a specific solvent. Therefore, application development of the material as a recyclable material is highly expected.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polylactic acid resin composition having excellent crystallinity and releasability.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, it has been found that a predetermined effect can be obtained by applying a predetermined amount of an amide compound having a specific structure. And completed the present invention based on such findings.

That is, the polylactic acid-based resin composition according to the present invention has the general formula (1) based on 100 parts by weight of the polylactic acid-based resin.
Alternatively, one or more amide compounds represented by the general formula (2) are compounded in an amount of 0.01 to 5 parts by weight.

R ^1- (CONH-R ² ) a (1) wherein R ¹ is a saturated or unsaturated aliphatic polycarboxylic acid residue having 2 to 30 carbon atoms, a saturated or unsaturated alicyclic group Represents a polycarboxylic acid residue or an aromatic polycarboxylic acid residue. R ² is an alkyl group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group or cycloalkenyl group having 3 to 12 carbon atoms, a phenyl group, a naphthyl group, an anthryl group, a formula (a), a formula (B), equation (c)
Or a group represented by the formula (d). a shows the integer of 2-6. ]

[0008]

Embedded image [Wherein, R ³ represents an alkyl group having 1 to 18 carbon atoms, and 2 carbon atoms.
Represents an alkenyl group having 18 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, a phenyl group or a halogen atom. b represents an integer of 1 to 5. ]

[0009]

Embedded image [In the formula, R ⁴ represents a linear or branched alkylene group having 1 to ⁴ carbon atoms. R ⁵ has the same meaning as R ³ described above. c
Represents an integer of 0 to 5. ]

[0010]

Embedded image [Wherein, R ⁶ has the same meaning as R ³ described above. d represents an integer of 1 to 5. ]

[0011]

Embedded image [Wherein, R ⁷ has the same meaning as R ⁴ described above, and R ⁸ has the same meaning as R ³ above. e represents an integer of 0 to 5. ]

Represents a ^{(NHCO-R 10) f (} 2) [ wherein, alicyclic polyamines residue or an aromatic polyamine residue of R ⁹ is a saturated or unsaturated 3 to 25 carbon atoms - [0012] R ^9. R ¹⁰ has the same meaning as R ² described above. f shows the integer of 2-6. ]

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the polylactic acid resin according to the present invention include polylactic acid (homopolymer of lactic acid), lactic acid and other monomers (specifically, hydroxycarboxylic acids and cyclic monomers). ) And mixtures thereof.

Examples of the lactic acid include L-lactic acid, D-lactic acid and mixtures thereof, and lactide which is a cyclic dimer of each of the above lactic acids, ie, L-lactide, D-lactide and mixtures thereof. it can. The lactic acid includes
DL-lactic acid can be used in combination as long as the crystallinity of the obtained polymer is not impaired (the maximum combined amount of DL-lactic acid used in combination is 20% by weight).

The hydroxycarboxylic acids used for the copolymerization include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid and 6-hydroxycaproic acid.

The cyclic monomers used for copolymerization include glycolide, β-propiolactone, D-β-butyrolactone, L-β-butyrolactone, D, L-β-butyrolactone, γ-butyrolactone, δ-valerolactone, ε
-Caprolactone and the like.

The polylactic acid-based resin is prepared, for example, by a method of ring-opening polymerization of lactide or lactide and another cyclic monomer in the presence or absence of a catalyst, or by direct dehydration polycondensation of lactic acid or lactic acid and hydroxycarboxylic acid. Can be prepared.

Examples of the catalyst include tin compounds such as tin octylate; titanium compounds such as tetraisopropyl titanate; zirconium compounds such as zirconium isopropoxide; antimony compounds such as antimony trioxide; aluminum isopropoxide; Any known catalysts for the polymerization of lactic acid, such as aluminum-based compounds, can be used.

The amount of the catalyst to be used is, for example, 0.001 to 0.5% by weight, preferably 0.1 to 0.3% by weight, based on lactic acid or lactide as a raw material.

The weight average molecular weight of the polylactic acid resin is preferably high as far as the moldability is possible, and more preferably 30,000 to 5,000,000. If the molecular weight is less than 30,000, the strength of the molded article becomes small, and is not suitable for practical use. Also,
Those having a molecular weight of 5,000,000 or more are inferior in moldability.

The polycarboxylic acid-based amide compound represented by the general formula (1) is prepared by synthesizing an aliphatic, alicyclic or aromatic polycarboxylic acid represented by the general formula (1a) or an anhydride thereof with the general formula (1). It can be easily prepared by amidating one or more aliphatic, alicyclic or aromatic monoamines represented by 1b) according to a conventionally known method.

[0022] ^{R 14 - (COOH) i (} 1a) [ wherein, R ¹⁴ and R ¹ of said, f is an s synonymous said a husband. ]

R ¹⁵ —NH ₂ (1b) wherein R ¹⁵ is as defined above for R ² . ]

Examples of the aliphatic polycarboxylic acids include oxalic acid, malonic acid, diphenylmalonic acid, succinic acid, phenylsuccinic acid, diphenylsuccinic acid, glutaric acid, 3,3
-Dimethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecandioic acid, 1,14-tetradecandioic acid, 1,18-octadecandioic acid, citric acid, methanetricarboxylic acid , Tricarballylic acid, propenetricarboxylic acid, pentanetricarboxylic acid, ethanetetracarboxylic acid, propanetetracarboxylic acid, pentanetetracarboxylic acid, butanetetracarboxylic acid (particularly 1,2,3,4-butanetetracarboxylic acid), dodecanetetra Carboxylic acid, pentanepentacarboxylic acid, tetradecanehexacarboxylic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ethyleneglycolbis (β-aminoethylether) N, N, N ′, N′-
Tetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediamine-N, N ', N'-triacetic acid,
1,3-diaminopropan-2-ol-N, N,
N ′, N′-tetraacetic acid, 1,2-diaminopropane-N,
Examples thereof include N, N ′, N′-tetraacetic acid, triethylenetetramine hexaacetic acid, nitrilotripropionic acid, 1,6-hexanediaminetetraacetic acid, and N- (2-carboxyethyl) iminodiacetic acid.

The alicyclic polycarboxylic acids include 1,2-
Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, cyclohexanetricarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, 5- (succinic acid ) -3-Methyl-3-cyclohexene-1,2-dicarboxylic acid, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid,
Cyclohexanehexacarboxylic acid, 5,6,9,10
-Tetracarboxytricyclo [6.2.2.0 ^2,7 ]
Dodeca-2,11-diene and its lower alkyl-substituted product (for example, methyl-substituted product at the 3-, 8-, 11- or 12-position), 1,2-cyclohexanediaminetetraacetic acid, 2,2
3,5-tricarboxycyclopentylacetic acid, 6-methyl-4-cyclohexene-1,2,3-tricarboxylic acid, 3,5,6-tricarboxynorbonene-2-acetic acid, thiobis (norbonene-2,3- Dicarboxylic acid),
Bicyclo [4.2.0] octane-3,4,7,8-tetracarboxylic acid, 1,1′-bicyclopropane-2,
2 ', 3,3'-tetracarboxylic acid, 1,2-bis (2,3-dimethyl-2,3-dicarboxycyclobutyl) ethane, pyrazine-2,3,5,6-tetracarboxylic acid, tricyclo [4.2.2.0 ^{2, 5]} decane-9
Ene-3,4,7,8-tetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid and lower alkyl-substituted products thereof (for example,
1-, 5-, 6- or 7-position methyl-substituted), 2,3
4,5,6,7,12,13-octahydrophenanthrene-3,4,5,6-tetracarboxylic acid and the like are exemplified.

Examples of the aromatic polycarboxylic acid include p-phenylene diacetic acid, p-phenylenediethane acid, phthalic acid,
4-tert-butylphthalic acid, isophthalic acid, 5-tert-
Butyl isophthalic acid, terephthalic acid, 1,8-naphthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid,
Diphenic acid, 3,3′-biphenyldicarboxylic acid, 4,
4'-biphenyldicarboxylic acid, 4,4'-binaphthyldicarboxylic acid, bis (3-carboxyphenyl) methane, bis (4-carboxyphenyl) methane, 2,2-
Bis (3-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) propane, 3,3′-sulfonyldibenzoic acid, 4,4′-sulfonyldibenzoic acid, 3,3′-oxydibenzoic acid 4,4′-oxydibenzoic acid, 3,3′-carbonyldibenzoic acid, 4,4 ′
-Carbonyl dibenzoic acid, 3,3'-thiodibenzoic acid,
4,4′-thiodibenzoic acid, 4,4 ′-(p-phenylenedioxy) dibenzoic acid, 4,4′-isophthaloyldibenzoic acid, 4,4′-terephthaloyldibenzoic acid, dithiosalicylic acid, benzenetricarboxylic acid, Benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid (particularly 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid), diphenylmethanetetracarboxylic acid, Perylenetetracarboxylic acid, naphthalenetetracarboxylic acid,
4,4′-dinaphthalic acid, benzidine-3,3′-dicarboxyl-N, N′-tetraacetic acid, diphenylpropanetetracarboxylic acid, anthracenetetracarboxylic acid, phthalocyanine tetracarboxylic acid, ethylene glycol-trimellitic diester, Benzenehexacarboxylic acid,
Glycerin-trimellitic acid triester and the like are exemplified.

Examples of the aliphatic monoamine include methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, isobutylamine, secondary butylamine, tertiary butylamine, n-amylamine, tertiary amylamine, hexylamine, heptylamine, n Octylamine, 2-ethylhexylamine, tertiary octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine,
Examples thereof include pentadecylamine, octadecylamine, octadecenylamine, and allylamine.

Examples of the alicyclic monoamine include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cyclobutylamine, cyclooctylamine, cyclododecylamine, etc., as well as those represented by formula (4) or (5). Compounds to be used.

[0029]

Embedded image [In the formula, R ¹⁶ represents an alkyl group, an alkenyl group, or an alkoxyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a halogen atom. j represents an integer of 1 to 5. ]

[0030]

Embedded image [In the formula, R ¹⁷ represents a linear or branched alkylene group having 1 to 4 carbon atoms. R ¹⁸ has the same meaning as R ¹⁶ described above. k
Represents an integer of 0 to 5. ]

The alicyclic monoamine represented by the general formula (4) includes methylcyclohexylamine, ethylcyclohexylamine, propylcyclohexylamine, isopropylcyclohexylamine, tert-butylcyclohexylamine, n-butylcyclohexylamine, isobutylcyclohexylamine , Sec-butylcyclohexylamine, n-amylcyclohexylamine, isoamylcyclohexylamine, sec-amylcyclohexylamine, tert-amylcyclohexylamine, hexylcyclohexylamine, heptylcyclohexylamine, octylcyclohexylamine, nonylcyclohexylamine, decylcyclohexylamine, Decylcyclohexylamine, dodecylcyclohexylamine, cyclohexylcyclo Hexylamine, phenylcyclohexylamine, dimethylcyclohexylamine,
Diethylcyclohexylamine, dipropylcyclohexylamine, diisopropylcyclohexylamine, di-n-butylcyclohexylamine, di-sec-butylcyclohexylamine, di-tert-butylcyclohexylamine, di-n-amylcyclohexylamine, di-
tert-amylcyclohexylamine, dihexylcyclohexylamine, trimethylcyclohexylamine, triethylcyclohexylamine, tripropylcyclohexylamine, triisopropylcyclohexylamine, tri-n-butylcyclohexylamine, tri-se
c-butylcyclohexylamine, tri-tert-butylcyclohexylamine, methoxycyclohexylamine, ethoxycyclohexylamine, dimethoxycyclohexylamine, diethoxycyclohexylamine, di-n-butoxycyclohexylamine, di-sec-butoxycyclohexylamine, di-tert -Butoxycyclohexylamine, trimethoxycyclohexylamine,
Examples thereof include tri-n-butoxycyclohexylamine, chlorocyclohexylamine, dichlorocyclohexylamine, methylchlorocyclohexylamine, trichlorocyclohexylamine, bromocyclohexylamine, dibromocyclohexylamine, and tribromocyclohexylamine.

The alicyclic monoamine represented by the general formula (5) includes cyclohexylmethylamine, methylcyclohexylmethylamine, dimethylcyclohexylmethylamine, trimethylcyclohexylmethylamine, methoxycyclohexylmethylamine, ethoxycyclohexylmethylamine, dimethoxycyclohexyl Methylamine, chlorocyclohexylmethylamine, dichlorocyclohexylmethylamine, α-cyclohexylethylamine, β-cyclohexylethylamine, methoxycyclohexylethylamine, dimethoxycyclohexylethylamine, chlorocyclohexylethylamine, dichlorocyclohexylethylamine, α-cyclohexylpropylamine, β-cyclohexylpropylamine , Γ-cyclohexyl Examples thereof include propylamine and methylcyclohexylpropylamine.

As the aromatic monoamine, aniline, 1
In addition to -naphthylamine, 2-naphthylamine, 1-aminoanthracene, and 2-aminoanthracene, a compound represented by the general formula (6) or the general formula (7) may be mentioned.

[0034]

Embedded image [Wherein, R ¹⁹ has the same meaning as R ¹⁶ described above. l represents an integer of 1 to 5. ]

[0035]

Embedded image [Wherein, R ²⁰ has the same meaning as R ¹⁷ described above, and R ²¹ has the same meaning as R ¹⁶ . m shows the integer of 0-5. ]

The aromatic monoamine represented by the general formula (6) includes toluidine, ethylaniline, propylaniline, cumidine, tert-butylaniline, n-butylaniline, isobutylaniline, sec-butylaniline,
n-amylaniline, isoamylaniline, sec-amylaniline, tert-amylaniline, hexylaniline, heptylaniline, octylaniline, nonylaniline, decylaniline, undecylaniline, dodecylaniline, cyclohexylaniline, aminodiphenyl, aminostyrene, dimethyl Aniline, diethylaniline, dipropylaniline, diisopropylaniline,
Di-n-butylaniline, di-sec-butylaniline,
Di-tert-butylaniline, trimethylaniline, triethylaniline, tripropylaniline, tri-tert-
Examples thereof include butylaniline, anisidine, ethoxyaniline, dimethoxyaniline, diethoxyaniline, trimethoxyaniline, tri-n-butoxyaniline, chloroaniline, dichloroaniline, trichloroaniline, bromoaniline, dibromoaniline, and tribromoaniline.

As the aromatic monoamine represented by the general formula (7), benzylamine, methylbenzylamine, dimethylbenzylamine, trimethylbenzylamine, methoxybenzylamine, ethoxybenzylamine, dimethoxybenzylamine, chlorobenzylamine, dichloroamine Benzylamine, α-phenylethylamine, β-phenylethylamine, methoxyphenylethylamine,
Dimethoxyphenylethylamine, chlorophenylethylamine, dichlorophenylethylamine, α-phenylpropylamine, β-phenylpropylamine, γ-
Examples thereof include phenylpropylamine and methylphenylpropylamine.

The polyamine amide compound represented by the general formula (2) includes an alicyclic or aromatic polyamine represented by the following general formula (2a) and a polyamine amide compound represented by the following general formula (2b).
It can be easily prepared by amidating a kind or two or more kinds of aliphatic, alicyclic or aromatic monocarboxylic acids according to a conventionally known method.

[0039] _{^{R 22 - (NH 2) n}} (2a) [ wherein, R ²² and said R ^9, n is f and respectively synonymous. ]

R ²³ —COOH (2b) wherein R ²³ has the same meaning as R ¹⁰ described above. ]

Examples of the alicyclic polyamine include 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexyl, and 4,4'-
Diamino-3,3'-dimethyldicyclohexyl, 4,
4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane,
1,3-bis (aminomethyl) cyclohexane, 1,4
-Bis (aminomethyl) cyclohexane, isophoronediamine, mensendiamine, melamine, 2,4,6-
Triaminopyrimidine, 1,3,5-triaminocyclohexane, 1,2,4-triaminocyclohexane,
Examples thereof include 1,2,4,5-tetraaminocyclohexane and the like.

Examples of the aromatic polyamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,6-diaminotoluene and 3,4-diamino Toluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine,
4,5-dimethyl-o-phenylenediamine, 2,4-
Diaminomesitylene, 2,3-diaminopyridine, 2,
6-diaminopyridine, 3,4-diaminopyridine,
1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,7-diaminonaphthalene, 9,10-diaminophenanthrene, 3,
3 ', 5,5'-tetramethylbenzidine, 3,3'-
Dimethyl-4,4'-diaminobiphenyl, 3,3'-
Dimethoxy-4,4'-diaminobiphenyl, 4,4 '
-Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane,
4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-xylysine, 4,4'-methylenedi-2,6-diethylaniline, 4,4'-diamino-
1,2-diphenylethane, 4,4′-diamino-2,
2'-dimethylbibenzyl, 4,4'-diaminostilbene, 3,4'-diamino-2,2-diphenylpropane, 4,4'-diamino-2,2-diphenylpropane, 4,4'-diaminodiphenyl ether , 3,4 '
-Diaminodiphenyl ether, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,
3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 4,4′-diaminobenzanilide, o
-Tolidine sulfone, 2,7-diaminofluorene,
3,7-diamino-2-methoxyfluorene, bis-p
-Aminophenylaniline, 1,3-bis (4-aminophenylpropyl) benzene, 1,4-bis (4-aminophenylpropyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4- Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] sulfone , 9,9-bis (4-aminophenyl) fluorene-1,2,4,5-tetraaminobenzene, 1,3,5-triaminobenzene, 1,
2,4-triaminobenzene, pararoseaniline,
Examples thereof include 2,4,6-triaminophenol, 3,3′-diaminobenzidine, tris (4-aminophenyl) methane and the like. However, xylylenediamine cannot achieve a predetermined effect.

As the aliphatic monocarboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid,
Caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, acrylic acid, crotonic acid, oleic acid, elaidic acid, sorbic acid , Linoleic acid, linoleic acid, pivalic acid and the like.

Examples of the alicyclic monocarboxylic acid include cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexenecarboxylic acid, cycloheptanecarboxylic acid, methylcyclopentanecarboxylic acid, and phenyl In addition to cyclopentanecarboxylic acid, butylcyclohexenecarboxylic acid, and methylcycloheptanecarboxylic acid, a compound represented by the general formula (8) or the general formula (9) may be mentioned.

[0045]

Embedded image [Wherein, R ²⁴ has the same meaning as R ¹⁶ described above. o shows the integer of 1-5. ]

[0046]

Embedded image [Wherein, R ²⁵ has the same meaning as R ¹⁷ described above, and R ²⁶ has the same meaning as R ²⁴ . p shows the integer of 0-5. ]

The alicyclic monocarboxylic acids represented by the general formula (8) include methylcyclohexanecarboxylic acid, ethylcyclohexanecarboxylic acid, propylcyclohexanecarboxylic acid, butylcyclohexanecarboxylic acid, pentylcyclohexanecarboxylic acid, and hexylcyclohexanecarboxylic acid. , Phenylcyclohexanecarboxylic acid, chlorocyclohexanecarboxylic acid, bromocyclohexanecarboxylic acid, dimethylcyclohexanecarboxylic acid, di-te
rt-butylcyclohexanecarboxylic acid, methoxycyclohexanecarboxylic acid, ethoxycyclohexanecarboxylic acid, dimethoxycyclohexanecarboxylic acid, diethoxycyclohexanecarboxylic acid, dichlorocyclohexanecarboxylic acid, trimethylcyclohexanecarboxylic acid, trimethoxycyclohexanecarboxylic acid, triethoxycyclohexanecarboxylic acid, etc. Is exemplified.

Examples of the alicyclic monocarboxylic acid represented by the general formula (9) include cyclohexylacetic acid, methylcyclohexylacetic acid, methoxycyclohexylacetic acid, cyclohexylpropionic acid, and cyclohexylbutyric acid.

As the aromatic monocarboxylic acid, in addition to benzoic acid, 1-naphthoic acid, 2-naphthoic acid and 9-carboxyanthracene, general formula (10) or general formula (1)
The compound represented by 1) is mentioned.

[0050]

Embedded image [Wherein, R ²⁷ has the same meaning as R ²⁴ described above. q shows the integer of 1-5. ]

[0051]

Embedded image [Wherein, R ²⁸ has the same meaning as R ²⁵ described above, and R ²⁹ has the same meaning as R ²⁴ . r shows the integer of 0-5. ]

The aromatic monocarboxylic acid represented by the general formula (10) includes methylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, butylbenzoic acid, p-tert-butylbenzoic acid, pentylbenzoic acid, and hexylbenzoic acid. Acid, phenylbenzoic acid, cyclohexylbenzoic acid, chlorobenzoic acid, bromobenzoic acid, methoxybenzoic acid, ethoxybenzoic acid, dimethylbenzoic acid, di-tert-butylbenzoic acid,
Dimethoxybenzoic acid, diethoxybenzoic acid, dichlorobenzoic acid, trimethylbenzoic acid, trimethoxybenzoic acid,
Examples include triethoxybenzoic acid.

The aromatic monocarboxylic acid represented by the general formula (11) includes phenylacetic acid, methylphenylacetic acid,
Examples include methoxyphenylacetic acid, phenylpropionic acid, and phenylbutyric acid.

Among the amide compounds according to the present invention, trimesic acid tris (t-butylamide), 1,4-cyclohexanedicarboxylic acid dianilide, 2,6-naphthalenedicarboxylic acid dicyclohexylamide, N, N'-dibenzoyl-1, 4-diaminocyclohexane, N,
Compounds such as N'-dicyclohexanecarbonyl-1,5-diaminonaphthalene are particularly recommended.

The total amount of the amide compound relative to 100 parts by weight of the polylactic acid resin is 0.01 to 5 parts by weight. 0.
When the amount is less than 01 parts by weight, the effect of improving the formability is not obtained because the crystallization promoting effect is insufficient. When the amount is more than 5 parts by weight, the transparency cannot be obtained or the amount is just as much as required. In any case, the reforming effect cannot be obtained, which is uneconomical.

The polylactic acid resin composition according to the present invention includes:
Depending on the intended use, a reinforcing agent and a filler can be appropriately compounded.

The reinforcing agent and filler are not particularly limited as long as a predetermined effect can be obtained. Specifically, carbon black, calcium carbonate, magnesium carbonate,
Barium sulfate, kaolin, calcined clay, talc, wollastonite, mica, aluminum silicate, calcium silicate, silicic acid, alumina, magnesium oxide, titanium oxide, boron nitride, carbon fiber, glass fiber, asbestos fiber, carbon fiber, Examples thereof include silica fibers, zirconia fibers, aramid fibers, potassium titanate fibers, and metal fibers.

Further, antioxidants (hindered amine compounds, benzophenone compounds, benzotriazole compounds, etc.), crystal nucleating agents, ultraviolet absorbers, pigments, dyes, antistatic agents, stabilizers (phenolic compounds, sulfur compounds, phosphorus compounds) Compounds, nitrogen compounds, etc.), plasticizers, other polymers, flame retardants,
Modifiers, lubricants [Recommended additives include C8-C
22 higher alcohols, higher fatty acids having 8 to 22 carbon atoms,
Higher fatty acid amides having 8 to 22 carbon atoms (specifically, methylenebisstearic acid amide, ethylenebisstearic acid amide, ethylenebisbalmitic acid amide, ethylenebisoleic acid amide), metals of higher fatty acids having 8 to 22 carbon atoms Salts (alkali metal salts, alkaline earth metal salts,),
Aliphatic hydrocarbons, waxes] and release agents.

The method of compounding the amide compound used in the present invention is not particularly limited, and may be a method of adding the compound during polymerization, dissolving or dispersing the amide compound in a predetermined solvent, and compounding the obtained solution or dispersion with the resin. After that, a method of removing the solvent (solution method), a method of melt-kneading with an extruder, a method of adding during injection molding, a method of dry blending, and a method combining these methods can be used.

Solvents applied in the solution method include:
Examples thereof include chloroform, dioxane, hexafluoroisopropanol, and dimethyl sulfoxide.

The polylactic acid-based resin composition thus obtained may be used as a container or stationery for cosmetics, daily necessities, food, miscellaneous goods (ballpoint pen, sharpener shaft and case, etc.), a scaffold for tissue regeneration as a medical material, a fracture fixing material, and the like. Used for applications such as biodegradable polymer materials.

[0062]

The present invention will be described below in detail with reference to Examples and Comparative Examples.

Examples 1 to 16 100 parts by weight of poly L-lactide having a number average molecular weight of 100,000 and 1.0 part by weight of a predetermined amide compound were mixed with a small amount of chloroform to form a paste. After removing the chloroform by drying under reduced pressure, cut into a disk shape,
It was inserted into an aluminum cell for DSC measurement, heated to 210 ° C. by DSC, held and melted for 3 minutes, and then cooled to 70 ° C. at a cooling rate of 5 ° C./min to determine the crystal onset temperature of poly L-lactide. Was. Table 1 shows the obtained results.

Next, 100 parts by weight of poly L-lactide having a number average molecular weight of 100,000 and 1.0 part by weight of an amide compound were mixed with a Henschel mixer, and the barrel temperature was adjusted to 180-2.
Melt and mix with a 25 mmφ single screw extruder set at 10 ° C,
Pelletized. Further, the obtained pellets were subjected to a barrel temperature of 180 to 210 ° C., a mold temperature of 30 ° C., an injection time of 15 seconds by an injection molding machine (mold clamping pressure: 40 tons, manufactured by Nissei Plastics Industry Co., Ltd.).
Molding was performed under the condition of a cooling time of 20 seconds to obtain a plate of 40 × 60 × 2 mm. At this time, the releasability from the mold was evaluated in the following three grades. Table 1 shows the obtained results. ◎: very good releasability, ○: good releasability, ×: poor releasability

Comparative Example 1 The crystallization start temperature and the releasability from the mold were determined in the same manner as in Example 1 except that no amide compound was added. Table 1 shows the obtained results.

[0066]

[Table 1]

[0067]

The polylactic acid-based resin composition of the present invention has greatly improved crystallinity and excellent mold releasability, so that a molding cycle can be shortened, and productivity by injection molding and the like is greatly increased. To improve. Further, the obtained molded product is useful as various containers and stationery as environmental protection materials, and biodegradable polymers.

Claims (3)

[Claims] 1 to 100 parts by weight of a polylactic acid-based resin, 0.01 to 5 parts by weight of one or more amide-based compounds represented by the general formula (1) or (2). A polylactic acid-based resin composition comprising: R ^1- (CONH-R ² ) a (1) wherein R ¹ is a saturated or unsaturated aliphatic polycarboxylic acid residue having 2 to 30 carbon atoms, a saturated or unsaturated alicyclic polycarboxylic acid Represents a residue or an aromatic polycarboxylic acid residue. R ² is an alkyl group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group or cycloalkenyl group having 3 to 12 carbon atoms, a phenyl group, a naphthyl group, an anthryl group, a formula (a), a formula (B), equation (c)
Or a group represented by the formula (d). a shows the integer of 2-6. ] [Wherein, R ³ represents an alkyl group having 1 to 18 carbon atoms, and 2 carbon atoms.
Represents an alkenyl group having 18 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, a phenyl group or a halogen atom. b represents an integer of 1 to 5. ] [In the formula, R ⁴ represents a linear or branched alkylene group having 1 to ⁴ carbon atoms. R ⁵ has the same meaning as R ³ described above. c
Represents an integer of 0 to 5. ] [Wherein, R ⁶ has the same meaning as R ³ described above. d represents an integer of 1 to 5. ] [Wherein, R ⁷ has the same meaning as R ⁴ described above, and R ⁸ has the same meaning as R ³ above. e represents an integer of 0 to 5. ^{] R 9 - (NHCO-R} 10) f (2) [ wherein, R ⁹ represents an alicyclic polyamines residue or an aromatic polyamine residue of a saturated or unsaturated 3 to 25 carbon atoms. R ¹⁰ has the same meaning as R ² described above. f shows the integer of 2-6. ] 2. The polylactic acid resin composition according to claim 1, wherein the polylactic acid resin is poly L-lactide. 3. An amide compound comprising tris (t-butylamide) trimesic acid, 1,4-cyclohexanedicarboxylic dianilide, 2,6-naphthalenedicarboxylic acid dicyclohexylamide, N, N′-dibenzoyl-1,
The polylactic acid-based resin composition according to claim 1, which is 4-diaminocyclohexane or N, N'-dicyclohexanecarbonyl-1,5-diaminonaphthalene.