JP2011174094A - Aliphatic or alicyclic polyester-based resin composition - Google Patents

Abstract

An aliphatic or cycloaliphatic polyester resin composition having excellent balance between rigidity and mechanical strength, weather resistance, and hydrolysis resistance is provided.
SOLUTION: A carbodiimide compound is 0.001 to 2 parts by weight of a hindered amine light stabilizer (B) having two or more hindered amine structures with respect to 100 parts by weight of an aliphatic or alicyclic polyester resin (A). Aliphatics comprising 0.01 to 10 parts by weight of (D), 1 to 50 parts by weight of filler (E), and preferably 0.001 to 2 parts by weight of UV absorber (C). Or an alicyclic polyester-type resin composition.
[Selection figure] None

Description

The present invention relates to an aliphatic or alicyclic polyester-based resin composition, and more particularly, an aliphatic or alicyclic polyester-based resin composition having excellent balance between rigidity and mechanical strength, weather resistance, and hydrolysis resistance. Related to things.

  Conventionally, a polycondensate or copolycondensate mainly composed of a structural repeating unit derived from an aliphatic or alicyclic diol component and an aliphatic or alicyclic dicarboxylic acid component, or a structural repeating unit derived from a hydroxycarboxylic acid component Aliphatic or alicyclic polyester-based resins such as polycondensates or copolycondensates mainly composed of polycondensates or polycondensates or copolycondensates mainly composed of structural repeating units derived from lactone components or / and lactide components It is attracting attention as a plastic that can be decomposed, and it is used for various packaging materials, agricultural materials, fishery materials, home appliance parts, automobile parts, etc. as molded articles such as films, sheets, containers and fibers, or its use has been attempted. .

  However, in each of these uses, it is required to be easily biodegradable at the stage of disposal, but during use it must have not only a balance between rigidity and mechanical strength, but also weather resistance and hydrolysis resistance. However, the above-mentioned aliphatic or alicyclic polyester resins having excellent biodegradability have not always been sufficient in long-term performance such as weather resistance and hydrolysis resistance.

  On the other hand, as a method for imparting hydrolysis resistance to an aliphatic or alicyclic polyester resin, a method of adding a carbodiimide compound is known (see, for example, Patent Document 1). Further, as a method for imparting weather resistance, a resin composition in which an ultraviolet absorber, an inorganic filler, and a hindered amine light stabilizer are added to an aliphatic or alicyclic polyester resin is known (for example, According to the inventor's study, however, the resin composition disclosed therein is still not sufficient in terms of the balance between rigidity and mechanical strength, weather resistance, and the like. It has been found.

JP 2003-3052 A JP 2003-147096 A

  The present invention has been made in view of the above-described prior art. Accordingly, the present invention provides an aliphatic or alicyclic polyester resin composition excellent in the balance between rigidity and mechanical strength, weather resistance, and hydrolysis resistance. The purpose is to provide goods.

  The present inventor has found that the above-mentioned problems can be solved in a combined system with a carbodiimide compound by using a specific hindered amine light stabilizer together with an inorganic filler in an aliphatic or alicyclic polyester resin. Therefore, the present invention provides 0.001 hindered amine light stabilizer (B) having two or more hindered amine structures with respect to 100 parts by weight of the aliphatic or alicyclic polyester resin (A). Aliphatic or alicyclic polyester resin composition comprising ˜2 parts by weight, 0.01 to 10 parts by weight of carbodiimide compound (D), and 1 to 50 parts by weight of filler (E) Is the gist.

  ADVANTAGE OF THE INVENTION According to this invention, the aliphatic or alicyclic polyester-type resin composition excellent in the balance of rigidity and mechanical strength, weather resistance, and hydrolysis resistance can be provided.

  The aliphatic or alicyclic polyester resin (A) constituting the aliphatic or alicyclic polyester resin composition of the present invention includes an aliphatic or alicyclic diol component and an aliphatic or alicyclic dicarboxylic acid component. A polycondensate and a copolycondensate mainly composed of structural repeating units derived from the above, a polycondensate and a copolycondensate composed mainly of structural repeating units derived from an aliphatic or alicyclic hydroxycarboxylic acid component, a lactone component or And / or polycondensates and copolycondensates mainly composed of structural repeating units derived from the lactide component.

  Here, specific examples of the aliphatic or alicyclic diol component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, diethylene glycol, triethylene glycol, Examples include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and the like. The carbon number is 3-10 Preferably is, 1,3-propanediol, 1,4-butanediol, more preferably 1,4-cyclohexanedimethanol, 1,4-butanediol is particularly preferred. Two or more of these may be used in combination.

  Specific examples of the aliphatic or alicyclic dicarboxylic acid component include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and undecaic acid. Dicarboxylic acid, dodecadicarboxylic acid, dimer acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and ester-forming derivatives such as alkyl esters and anhydrides of about 1 to 4 carbon atoms of these dicarboxylic acids, etc. Among them, it is preferable that the number of carbon atoms is 4 to 12, and oxalic acid, adipic acid, sebacic acid, and alkyl esters and anhydrides of these dicarboxylic acids are more preferable. Particularly preferred are acids and their alkyl esters and anhydrides. Two or more of these may be used in combination.

  Examples of the aliphatic or alicyclic hydroxycarboxylic acid component include glycolic acid, lactic acid, 2-hydroxy-n-butyric acid, 2-hydroxy-3-methyl-n-butyric acid, and 2-hydroxy-3,3. -Dimethyl-n-butyric acid, 3-hydroxy-n-butyric acid, 4-hydroxy-n-butyric acid, 2-hydroxy-n-valeric acid, 3-hydroxy-n-valeric acid, 4-hydroxy-n-valeric acid, 5-hydroxy-n-valeric acid, 2-hydroxy-n-hexanoic acid, 3-hydroxy-n-hexanoic acid, 4-hydroxy-n-hexanoic acid, 5-hydroxy-n-hexanoic acid, 6-hydroxy-n -Hexanoic acid, 1-hydroxy-1-cyclopropanecarboxylic acid, 2-hydroxycyclohexanecarboxylic acid, 3-hydroxycyclohexanecarboxylic acid, 4-hydroxycyclohexane Examples include xanthcarboxylic acids, alkyl esters having about 1 to 4 carbon atoms, and intramolecular esters of these hydroxycarboxylic acids, and when optical isomers exist in these, D-form, L-form, or Any of the racemates may be used. Of these, glycolic acid and lactic acid are particularly preferred. Two or more of these may be used in combination.

  Examples of the lactone component include propiolactone, butyrolactone, valerolactone, caprolactone, and laurolactone. Examples of the lactide component include cyclic multimers of the hydroxycarboxylic acid. Two or more of these may be used in combination.

  These aliphatic or alicyclic polyester resins may be used as copolycondensation components, for example, aromatic diols such as 2,2-bis (4′-hydroxyphenyl) propane, aromatics such as terephthalic acid and isophthalic acid. Aromatic oxycarboxylic acids such as dicarboxylic acid and hydroxybenzoic acid, and trimellitic acid, trimesic acid, pyromellitic acid, benzophenone tetracarboxylic acid, hydroxyisophthalic acid, hydroxyterephthalic acid, gallic acid, or anhydrides thereof A structural repeating unit derived from an aromatic compound such as an aromatic polyvalent carboxylic acid or its anhydride, or an aliphatic or alicyclic polyvalent polyfunctional or higher functional group such as trimethylolethane, trimethylolpropane, glycerol, pentaerythritol Alcohol, tricarballylic acid, cyclopentanetetracarbo Trifunctional or higher functional aliphatic or alicyclic polycarboxylic acid such as acid or anhydride thereof, or anhydride thereof, and 3 such as apple succinic acid, hydroxyglutaric acid, hydroxymethylglutaric acid, tartaric acid, succinic acid, etc. A structural repeating unit derived from a functional or higher aliphatic or alicyclic hydroxycarboxylic acid or the like may be contained in a proportion of 5 mol% or less, preferably 2.5 mol% or less. Among these, trifunctional or higher aliphatic hydroxycarboxylic acids such as apple succinic acid, hydroxyglutaric acid, hydroxymethylglutaric acid, tartaric acid and succinic acid are preferable, and apple succinic acid, tartaric acid and succinic acid are particularly preferable.

  Among these aliphatic or alicyclic polyester-based resins, in the present invention, polycondensation mainly comprising constituent repeating units derived from an aliphatic or alicyclic diol component and an aliphatic or alicyclic dicarboxylic acid component. And a copolycondensate are preferred, and the constituent repeating unit mainly composed of the diol component and the dicarboxylic acid component and derived from the aliphatic or alicyclic hydroxycarboxylic acid component is 0.001 mol% or more, and further is preferably 0.00. It is preferably contained in a proportion of 01 mol% or more, particularly 0.1 mol% or more, 30 mol% or less, more preferably 20 mol% or less, and particularly preferably 10 mol% or less.

  The polycondensates and copolycondensates mainly composed of structural repeating units derived from the aliphatic or alicyclic diol component and the aliphatic or alicyclic dicarboxylic acid component are the aliphatic or alicyclic diol component and the fatty acid. A melt polycondensation method in which an aliphatic or alicyclic dicarboxylic acid component is subjected to an esterification reaction or a transesterification reaction, together with the copolycondensation component used as necessary, in the absence of solvent and under reduced pressure, Alternatively, it is produced by a known method such as a solution heating dehydration polycondensation method using an organic solvent, but the melt polycondensation method is preferred from the viewpoints of economy and simplicity of the production process.

  That is, the aliphatic or cycloaliphatic diol component, the aliphatic or cycloaliphatic dicarboxylic acid component, and the copolycondensation component used as necessary are mixed with stirring, under normal pressure to increased pressure. The esterification reaction under heating, or the ester exchange reaction in the presence of a transesterification catalyst, and then the obtained esterification reaction product or the polyester low molecular weight product as the transesterification reaction product is preferably Is subjected to melt polycondensation in the presence of a polycondensation catalyst under normal pressure to gradually reduced pressure under heating.

  At that time, the ratio of the aliphatic or alicyclic diol component and the aliphatic or alicyclic dicarboxylic acid component used is usually 0.8 to 1 mol of the latter dicarboxylic acid component. 1.5 mol, preferably 0.9 to 1.3 mol, more preferably 0.9 to 1.2 mol, and the preferred proportion of the hydroxycarboxylic acid component used as the copolycondensation component is: It is preferable to set it as 0.001-30 mol% with respect to all the components, It is more preferable to set it as 0.01-20 mol%, It is especially preferable to set it as 0.1-10 mol%.

  The esterification reaction or transesterification reaction is usually at a temperature of about 150 to 260 ° C., preferably about 180 to 250 ° C., usually under an inert gas atmosphere such as nitrogen or argon, and usually a pressure of normal pressure to 10 kPa. The reaction time is usually about 1 to 10 hours, preferably about 1 to 4 hours under normal pressure.

  The melt polycondensation is preferably performed in the presence of a polycondensation catalyst, usually at a temperature of about 150 to 260 ° C., preferably about 180 to 250 ° C., usually under a reduced pressure of about 10 to 1,400 Pa, preferably about 10 to 400 Pa. The time is usually about 2 to 15 hours, preferably about 2 to 10 hours.

  In addition, the polycondensation catalyst in the melt polycondensation is a catalyst conventionally used as a polyester polycondensation catalyst. Generally, it is a periodic table in which a group 1 to group 14 metal element excluding hydrogen and carbon is used. For example, one or more metal elements selected from the group consisting of titanium, zirconium, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium, and potassium And organic compounds such as carboxylates, alkoxy salts, organic sulfonates and β-diketonates, inorganic compounds such as oxides and halides, and mixtures thereof.

  In these, the compound containing any metallic element of titanium, a zirconium, germanium, zinc, aluminum, magnesium, or calcium, and those mixtures are preferable, and especially a titanium compound and a germanium compound are preferable. The catalyst is preferably used as a solution dissolved in a solvent or dissolved in an ester low polymer or polyester from the viewpoint of polymerization rate.

  The amount of these polycondensation catalysts added is usually 5 to 30,000 ppm, preferably 10 to 1,000 ppm, more preferably 10 to 250 ppm, and particularly preferably 10 to 130 ppm as the amount of metal relative to the polyester resin to be produced. . Too much catalyst is not only economically disadvantageous but also tends to reduce the thermal stability of the resulting polymer. If too little is used, the polymerization activity is lowered, and accordingly the polymer is not produced during polymer production. Degradation tends to be induced. The addition timing of the polycondensation catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added at the time of charging the raw materials or may be added at the start of pressure reduction.

  In the present invention, a known vertical or horizontal stirred tank reactor can be used as a reaction apparatus for producing the aliphatic or alicyclic polyester resin. For example, melt polycondensation is carried out in two stages, an esterification or transesterification process and a reduced pressure polycondensation process, using the same or different reactors, and a vacuum pump and a reactor are connected as a reduced pressure polycondensation reactor. A method using a stirred tank reactor equipped with an exhaust pipe for decompression can be mentioned. In addition, a condenser is connected between the vacuum exhaust pipe connecting the vacuum pump and the reactor, and the volatile components and unreacted monomers generated during the polycondensation reaction are recovered by the condenser. Is preferred.

  In the present invention, the aliphatic or alicyclic polyester-based resin has a reduced viscosity (measured at 30 ° C. in a phenol / tetrachloroethane (weight ratio 1/1) mixed solvent in order to obtain a practically sufficient mechanical strength. ηsp / C) is usually 1.5 or more, preferably 1.6 or more, and particularly preferably 1.7 or more. Moreover, from the viewpoints of ease of extraction from the reaction apparatus after the polycondensation reaction of the polyester resin and ease of molding, it is usually 6.0 or less, preferably 5.0 or less. A value of 0 or less is particularly preferred.

  In the present invention, the aliphatic or alicyclic polyester-based resin includes, for example, the aliphatic or alicyclic diol component and the aliphatic or alicyclic dicarboxylic acid in order to make the reduced viscosity range. A method of increasing the molecular weight by including a structural repeating unit derived from the aliphatic or alicyclic oxycarboxylic acid in a polycondensate or a copolycondensate mainly composed of a structural repeating unit derived from the component, or Addition of isocyanate compound as a coupling agent in the molten state to polyester diol whose terminal is substantially a hydroxyl group to increase the molecular weight by urethane bond, other amide bond, carbonate bond, ether bond, etc. A method of increasing the molecular weight or the like may be employed.

  The aliphatic or alicyclic polyester-based resin has a high crystallization rate, and the half-value width of the exothermic peak based on crystallization when cooled at 10 ° C./min in a differential scanning calorimeter is usually 15 ° C or lower, preferably 10 ° C or lower, particularly preferably 8 ° C or lower.

  The aliphatic or alicyclic polyester-based resin has a melt flow rate measured at 190 ° C. and 21.18 N of usually 0.1 g / 10 min or more and preferably 100 g / 10 min or less. It is more preferably 50 g / 10 min or less, particularly preferably 30 g / 10 min or less.

  The hindered amine light stabilizer (B) constituting the aliphatic or alicyclic polyester resin composition of the present invention must have at least two hindered amine structures, and has only one hindered amine structure. With the light stabilizer, the effect of the present invention cannot be obtained.

  Here, as the hindered amine structure, four hydrogen atoms bonded to the 2nd and 6th carbon atoms of piperidine are alkyl groups, preferably a linear alkyl group having 1 to 4 carbon atoms, particularly preferably methyl. The hindered amine light stabilizer in the present invention having a structure substituted with a group is preferably a compound having a partial structure represented by the following general formula (I).

[In the formula (I), R ¹ represents an alkyl group, an alkoxy group, an acyl group, or a hydrogen atom. ]

Here, the alkyl group of R ¹ and the acyl group preferably have 1 to 4 carbon atoms, and the alkoxy group preferably has 1 to 8 carbon atoms. These may further have a substituent.

  As the hindered amine light stabilizer (B) having two or more partial structures represented by the general formula (I), specifically, for example, bis (2,2,6,6-tetramethyl-4- Piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di-t-butyl-4-hydroxyphenyl) -2-n-butyl-bis (2,2,6,6-tetramethyl-4-piperidyl) malonate, 2- (3,5-di -T-butyl-4-hydroxyphenyl) -2-n-butyl-bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, 2- (3,5-di-t-butyl- 4-hydroxybenzyl) -2-n Butyl-bis (2,2,6,6-tetramethyl-4-piperidyl) malonate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl-bis (1, 2,2,6,6-pentamethyl-4-piperidyl) malonate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1 , 2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, mixed (2,2,6,6-tetramethyl-4-piperidyl / tridecyl)- 1,2,3,4-butanetetracarboxylate, mixed (1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate , Mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro [5 .5] Undecane] diethyl} -1,2,3,4-butanetetracarboxylate, mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′- Tetramethyl-3,9- [2,4,8,10-tetraoxaspiro [5.5] undecane] diethyl} -1,2,3,4-butanetetracarboxylate, 1,2-bis (3- Oxo-2,2,6,6-tetramethyl-4-piperidyl) ethane, 1- (3,5-di-tert-butyl-4-hydroxyphenyl) -1,1-bis (2,2,6, 6-tetramethyl-4-piperidyloxycarbonyl) pentane, poly [ -Oxyethylene (2,2,6,6-tetramethyl-1,4-piperidyl) oxysuccinyl], poly [2- (1,1,4-trimethylbutylimino) -4,6-triazinediyl- (2 , 2,6,6-tetramethyl-4-piperidyl) iminohexamethylene- (2,2,6,6-tetramethyl-4-piperidyl) imino], N, N′-bis (3-aminopropyl) ethylenediamine -2,4-bis [N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate and its N-methyl Examples thereof include polycondensates of compounds, oxalic acid and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine. Among these, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl- Bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate is particularly preferred.

  In the aliphatic or alicyclic polyester resin composition of the present invention, the content of the hindered amine light stabilizer (B) is 100 parts by weight of the aliphatic or alicyclic polyester resin (A). Therefore, it is essential that the amount is 0.001 part by weight or more, preferably 0.005 part by weight or more, and particularly preferably 0.01 part by weight or more. Further, it is essential that it is 2 parts by weight or less, preferably 1 part by weight or less, particularly preferably 0.5 part by weight or less. If the content of the hindered amine light stabilizer (B) is less than the above range, the weather resistance as a composition will be inferior. On the other hand, if it exceeds the above range, the surface appearance as a molded product of the composition will be poor due to bleeding out. Become.

  The aliphatic or cycloaliphatic polyester resin composition of the present invention further contains an ultraviolet absorber (C) in addition to the hindered amine light stabilizer (B) contained for the purpose of imparting weather resistance. Is preferred. As the ultraviolet absorber (C), among the ultraviolet absorbers such as benzophenone series, benzotriazole series, salicylic acid series, and cyanoacrylate series, a benzotriazole series ultraviolet absorbent is preferable. (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-amyl-2-hydroxy Phenyl) benzotriazole, 2- (5-t-octyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- [ 2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- ( 4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxy-phenol, methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yne)- 4-hydroxyphenyl] propionate and a condensation product of polyethylene glycol and the like. Among these, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (4,6-diphenyl-1,3,5-triazine- 2-yl) -5-hexyloxy-phenol is particularly preferred.

  In the aliphatic or alicyclic polyester-based resin composition of the present invention, the content of the ultraviolet absorber (C) is 0. 0 parts by weight with respect to 100 parts by weight of the aliphatic or alicyclic polyester-based resin (A). The amount is preferably 001 parts by weight or more, more preferably 0.005 parts by weight or more, and particularly preferably 0.01 parts by weight or more. Further, it is preferably 2 parts by weight or less, more preferably 1 part by weight or less, and particularly preferably 0.5 part by weight or less. If the content of the ultraviolet absorber (B) is less than the above range, the weather resistance as a composition tends to be inferior. On the other hand, if it exceeds the above range, the surface appearance as a molded article of the composition tends to be poor due to bleeding out. It becomes.

  The carbodiimide compound (D) constituting the aliphatic or alicyclic polyester resin composition of the present invention is a compound having one or more carbodiimide groups in the molecule. Such a carbodiimide compound is used as a catalyst, for example. It can be synthesized by using an organophosphorus compound or an organometallic compound and subjecting the isocyanate compound to a decarboxylation condensation reaction in a solvent-free or inert solvent at a temperature of 70 ° C. or higher.

  In the present invention, specific examples of the carbodiimide compound (D) include dimethylcarbodiimide, diisopropylcarbodiimide, diisobutylcarbodiimide, di-t-butylcarbodiimide, t-butylisopropylcarbodiimide, dioctylcarbodiimide, dicyclohexylcarbodiimide, and diphenylcarbodiimide. Monocarbodiimide compounds such as di-β-naphthylcarbodiimide and the like, as well as, for example, US Pat. No. 2,941,956, Japanese Examined Patent Publication No. 47-33279, J. Pat. Org. Chem. 28, p2069-2075 (1963), and Chemical Review 1981, 81, No. 4, p. And polycarbodiimide compounds produced by the method described in 619-621 and the like. Among these, diisopropylcarbodiimide, dicyclohexylcarbodiimide, polycarbodiimide, and the like are preferable in terms of industrial availability.

  In addition, as an organic diisocyanate which is a manufacturing raw material of a polycarbodiimide compound, specifically, for example, 1,5-naphthalene 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, mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, xylylene diisocyanate, tetra Aromatic diisocyanates such as methylxylylene diisocyanate, 2,6-diisopropylphenyl isocyanate, 1,3,5-triisopropylbenzene-2,4-diisocyanate, cyclohexane-1, - diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, alicyclic diisocyanates such as methylcyclohexane diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate, as well as mixtures thereof and the like. In addition, when synthesizing these polycarbodiimide compounds, active hydrogen-containing compounds capable of reacting with monoisocyanates and other terminal isocyanate groups can be used to control the degree of polymerization, and compounds used for such purposes. As monoisocyanate compounds such as phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate, methanol, ethanol, phenol, cyclohexanol, N-methylethanolamine, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl Hydroxyl-containing compounds such as ether, diethylamine, dicyclohexylamine, β-naphthylamine, cyclohexylamine Examples thereof include amino group-containing compounds, carboxyl group-containing compounds such as succinic acid, benzoic acid, and cyclohexane acid, mercapto group-containing compounds such as ethyl mercaptan, allyl mercaptan, and thiophenol, and various epoxy group-containing compounds. .

  The carbodiimide compound in the present invention is preferably a polycarbodiimide compound, and the degree of polymerization is preferably 2 or more, more preferably 4 or more, and preferably 40 or less, preferably 20 or less. More preferably. If the degree of polymerization is too large, dispersibility in the composition will be insufficient, and for example, it may cause poor appearance in the film.

  The carbodiimidization catalyst used in the decarboxylation condensation reaction of organic diisocyanate includes organic phosphorus compounds and organometallic compounds represented by the general formula M (OR) n (where M is titanium, sodium, potassium, vanadium, Metal atoms such as tungsten, hafnium, zirconium, lead, manganese, nickel, calcium, barium, R represents an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and n represents a metal atom M represents the valence that M can take.) Is preferred. Examples of the organic phosphorus compounds include 3-methyl-1-phenyl-2-phospholene-1-oxide, 3-methyl-1-ethyl-2-phospholene-1-oxide, and 1,3-dimethyl-2-phospholene. Phosphorene oxides such as -1-oxide, 1-phenyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 1-methyl-2-phospholene-1-oxide, and the like The double bond isomers can be exemplified. Of these, 3-methyl-1-phenyl-2-phospholene-1-oxide, which is easily available industrially, is particularly preferable. Among organometallic compounds, titanium, hafnium, and zirconium alkoxides are preferred because of their high activity.

  In the aliphatic or alicyclic polyester resin composition of the present invention, the content of the carbodiimide compound (D) is 0.000 part by weight with respect to 100 parts by weight of the aliphatic or alicyclic polyester resin (A). It is essential that the content is 01 parts by weight or more, preferably 0.05 parts by weight or more, and particularly preferably 0.1 parts by weight or more. Further, it must be 10 parts by weight or less, preferably 5 parts by weight or less, and particularly preferably 3 parts by weight or less. If the content of the carbodiimide compound (E) is less than the above range, the hydrolysis resistance of the composition will be reduced. On the other hand, if the content exceeds the above range, the addition effect will be saturated, and the effect will be commensurate with the increase in the addition amount. I can't get it.

  The filler (E) constituting the aliphatic or alicyclic polyester resin composition of the present invention may be either inorganic or organic. Inorganic fillers include oxides of metals such as magnesium, calcium, barium, zinc, zirconium, molybdenum, silicon, antimony, titanium, hydrates (hydroxides), sulfates, carbonates, silicates, And their double salts, and mixtures thereof. Specifically, for example, aluminum oxide (alumina), its hydrate, calcium hydroxide, magnesium oxide (magnesia), magnesium hydroxide, zinc oxide (zinc white), trilead tetroxide (lead red), hydroxy carbonate Lead (white lead), magnesium carbonate, calcium carbonate, basic magnesium carbonate, white carbon, mica, talc, glass fiber, glass powder, glass beads, clay, diatomaceous earth, silicon oxide (silica), wollastonite, iron oxide, Examples thereof include antimony oxide, titanium oxide (titania), lithopone, pumice powder, aluminum sulfate (gypsum, etc.), zirconium silicate, barium carbonate, dolomite, molybdenum disulfide, iron sand and the like. Examples of organic fillers include cellulose and starch, and specific examples include cellulose powder, wood powder, waste paper powder, rice husk powder, starch, and plasticized starch.

  Among these fillers, those having a powder form and a flat form preferably have a diameter or size of 10 μm or less, more preferably 5 μm or less, and particularly preferably 3 μm or less. Moreover, in the fibrous material, the diameter is preferably 1 to 100 μm, more preferably 1 to 50 μm, and the length is preferably 20 to 1000 μm, and preferably 20 to 300 μm. Further preferred. Among these fillers, flat (flaky) and powder are particularly preferable. Among the above fillers, inorganic flat fillers are particularly suitable. Specifically, trioctahedrals represented by montmorillonite and dioctahedral smectite represented by beidellite, hectorite and sabonite. Smectites such as smectite, vermiculites such as dioctahedral vermiculite, trioctahedral vermiculite, teniolite, tetrasilicon mica, mascobite, illite, sericite, phlobitite, biotite and other mica, and talc Is mentioned. These fillers may be produced as natural minerals or may be obtained by a synthesis method such as hydrothermal synthesis, melting method or solid phase method.

  In the aliphatic or alicyclic polyester resin composition of the present invention, the content of the filler (E) is 1 part by weight with respect to 100 parts by weight of the aliphatic or alicyclic polyester resin (A). It is essential that the amount is at least 2 parts by weight, particularly 5 parts by weight or more. Moreover, it is essential that it is 50 parts by weight or less, preferably 40 parts by weight or less, and particularly preferably 30 parts by weight or less. If the content of the filler (E) is less than the above range, the rigidity of the composition is inferior. On the other hand, if it exceeds the above range, the mechanical strength, particularly the impact strength, is lowered.

  In the present invention, the filler (E) may be surface-treated with a coupling agent in advance. Examples of the coupling agent include silane coupling agents, titanate coupling agents, and aluminate coupling agents. Examples of the silane coupling agent include triethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-glucidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Examples include 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl oris (dioctyl borophosphate), isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate. Tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl bisphosphate) oxyacetate titanate, bis (dioctyl bisphosphate) ethylene titanate, isopropyl trioctanoyl titanate, Isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacrylate Titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate. Examples of the aluminate coupling agent include acetoalkoxyaluminum diisopropylate.

  The aliphatic or alicyclic polyester-based resin composition of the present invention includes, as essential components, the aliphatic or alicyclic polyester-based resin (A), the hindered amine light stabilizer (B), the carbodiimide-based compound ( D), the filler (E), and the ultraviolet absorber (C) as an optional component, as long as the effects of the present invention are not impaired, other biodegradable resins such as aromatic polyesters, polyamides, Polyvinyl alcohol, cellulose ester and the like may be contained, and for the purpose of adjusting the processability and the physical properties of the molded body as a molded body, heat stabilizers, plasticizers, lubricants, antiblocking agents, Additives such as a nucleating agent, a crosslinking agent, a foaming agent, and a coloring agent may be contained.

  The method for preparing the aliphatic or alicyclic polyester resin composition of the present invention is not particularly limited, and after dry blending other components together with the aliphatic or alicyclic polyester resin pellets, melt kneading with an extruder. In addition, it may be pelletized and used for molding. Also, a high-concentration master batch is prepared in advance for each component, and after the master batch is dry blended with an aliphatic or alicyclic polyester resin pellet, It is good also as melt-kneading with an extruder, pelletizing and using for shaping | molding, or after dry blending, supplying directly to a shaping | molding machine and preparing a resin composition and obtaining a molded object.

  As the molding method of the aliphatic or alicyclic polyester resin composition of the present invention, a conventional molding method employed in conventional thermoplastic resins such as press molding, extrusion molding, injection molding, hollow molding, and the like can be applied. The laminate can also be formed by a conventional method. Moreover, it can also be set as a uniaxial or biaxially stretched product, in which case, stretching is usually performed at a stretching temperature in the range of 30 ° C. to 110 ° C., with a stretching ratio in the range of 0.6 to 10 times in the longitudinal and lateral directions. To do. At that time, after stretching, heat treatment may be performed by a method of blowing hot air, a method of irradiating infrared rays, a method of irradiating microwaves, a method of contacting on a heat roll, or the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded. In addition, the aliphatic or alicyclic polyester resin (A), hindered amine light stabilizer (B), ultraviolet absorber (C), carbodiimide compound (D) used in the following Examples and Comparative Examples, and The filler (E) is shown below.

<Aliphatic or alicyclic polyester resin (A)>
A-1: 134 kg of oxalic acid, 121 liters of 1,4-butanediol, and 1 germanium oxide were added to a reaction vessel having a capacity of 1 m ³ equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer, and a pressure reducing port. 7.21 kg of 90% DL lactic acid aqueous solution dissolved in weight% was charged. The contents of the container were stirred and a nitrogen gas atmosphere was started. The reaction was started at 120 ° C., and the temperature was raised to 200 ° C. over 1 hour and 40 minutes. Subsequently, the temperature was raised to 230 ° C. over 1 hour and 25 minutes and the pressure was reduced to 133 Pa. Polymerization was performed at 230 ° C. and 133 Pa for 4 hours and 20 minutes to obtain an aliphatic polyester resin (A-1). The obtained aliphatic polyester resin (A-1) had a reduced viscosity (ηsp / C) of 2.3 measured by the following method, a half-value width of 7.5 ° C. of an exothermic peak based on crystallization, and a melt flow rate. It was 4.2 g / 10 min.

<Reduced viscosity (ηsp / C)>
Using an Ubbelohde viscosity tube, measurement was performed at 30 ° C. at a concentration of 0.5 g / dl in a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1).
<Half-width of exothermic peak based on crystallization>
Using a differential scanning calorimeter (“DSC7” manufactured by PerkinElmer), 10 mg of sample was heated and melted under a nitrogen stream at a flow rate of 50 mL / min, then cooled at a rate of 10 ° C./min, and heat generated by crystallization. The peak was recorded and the half width was calculated.
<Melt flow rate>
The measurement was performed at a temperature of 190 ° C. and a load of 21.18N.

<Hindered amine light stabilizer (B)>
B-1: 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl-bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate (Ciba・ Specialty Chemicals "Tinuvin 144")
B-2: Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (“Sanol LS765” manufactured by Sankyo Lifetech Co., Ltd.)
B-3 (for comparative example): Compound having the following structure (“Sanol LS440” manufactured by Sankyo Lifetech Co., Ltd.)

  B-4 (for comparative example): Compound having the following structure (“Sanol LS2626” manufactured by Sankyo Lifetech Co., Ltd.)

<Ultraviolet absorber (C)>
C-1: 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxy-phenol (“Tinvin 1577FF” manufactured by Ciba Specialty Chemicals)
C-2: 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole (“Tinuvin 234” manufactured by Ciba Specialty Chemicals)
<Carbodiimide compound (D)>
D-1: polycarbodiimide obtained by condensation of dicyclohexylmethane-4,4′-diisocyanate (degree of polymerization: 8 to 12, softening temperature: 70 ° C., thermal decomposition temperature: 340 ° C.)
<Filler (E)>
E-1: Talc ("PKP-53S" manufactured by Fuji Talc)

Examples 1-5, Comparative Examples 1-9
Aliphatic or alicyclic polyester resin (A), hindered amine compound (B), ultraviolet absorber (C), carbodiimide compound (D), and filler (E) are blended as shown in Table 1. , Melt-kneaded at 190 ° C in a twin screw extruder, pelletized, and injection molded at 200 ° C to produce test pieces, tensile properties, bending properties, impact resistance, weather resistance, and hydrolysis resistance Were measured and evaluated by the methods shown below, and the results are shown in Table 1.

<Tensile properties>
Based on JISK6781, the tensile strength at break and tensile elongation at break were measured.
<Bending characteristics>
Based on JISK7113, the bending elastic modulus and bending strength were measured.
<Impact strength>
Izod impact strength was measured in accordance with JISK7110.
<Wear resistance>
Tensile fracture after 200 hours of irradiation at 63 ° C (black panel temperature) and no rain using a sunshine super long life weather meter "WEL-300L type" manufactured by Suga Test Instruments, using a test piece for measuring tensile properties The elongation was measured and the retention rate relative to the initial value was calculated.
<Hydrolysis resistance>
Using the test piece for measuring tensile properties, the tensile elongation at break after being held at 50 ° C. and 90% RH for 400 hours was measured, and the holding ratio relative to the initial value was calculated.

  ADVANTAGE OF THE INVENTION According to this invention, the aliphatic or alicyclic polyester-type resin composition excellent in the balance of rigidity and mechanical strength, weather resistance, and hydrolysis resistance can be provided, and this resin composition is plastic. For example, film-shaped, sheet-shaped, fiber-shaped, tray-shaped, bottle-shaped, pipe-shaped, and other specific shapes, etc., and biodegradable packaging materials and agricultural materials. It is suitably used as civil engineering materials, building materials, fishery materials, automobile parts, home appliance parts, other industrial materials, and the like.

Claims (5)

  0.001 to 2 parts by weight of a hindered amine light stabilizer (B) having two or more hindered amine structures and 100 parts by weight of an aliphatic or alicyclic polyester resin (A) and a carbodiimide compound (D) An aliphatic or alicyclic polyester resin composition comprising 0.01 to 10 parts by weight and a filler (E) in a proportion of 1 to 50 parts by weight.   The hindered amine light stabilizer (B) having two or more hindered amine structures is bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate or 2- (3,5-di-t- The aliphatic or alicyclic polyester resin according to claim 1, which is butyl-4-hydroxybenzyl) -2-n-butyl-bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate. Composition.   The aliphatic or alicyclic polyester resin composition according to claim 1 or 2, wherein the carbodiimide compound (D) is a polycarbodiimide compound having a polymerization degree of 2 to 40.   Furthermore, the aliphatic or alicyclic polyester-type resin composition in any one of Claims 1 thru | or 3 formed by containing 0.001-2 weight part of ultraviolet absorbers (C).   The ultraviolet absorber (C) is 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole or 2- (4,6-diphenyl-1,3 , 5-triazin-2-yl) -5-hexyloxy-phenol, The aliphatic or alicyclic polyester resin composition according to claim 4.