JPH115849A - Resin composition and its molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aliphatic polyester molded product capable of exhibiting transparency and heat resistance (high crystallization) at the same time by adding a specific organic compound to an aliphatic polyester, molding the aliphatic polyester with added compound, and crystallizing the molded product. SOLUTION: The objective molded product is obtained by molding an aliphatic polyester composition comprising (A) an aliphatic polyester and (B) at least one kind of organic compound selected from a group of organic compounds having 80-300 deg.C melting point and 10-100 cat/K/mol melting entropy as a transparent nucleic agent, and crystallizing the obtained molded product at the molding time or after molding. The component B is preferably a carboxylic acid amide, an aliphatic carboxylic acid amide, an aromatic carboxylic acid amide, and an alicyclic carboxylic acid amide, etc. The aliphatic polyester molding product having both transparency and crystallinity imparted thereto can be provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a molded article having both transparency and heat resistance from an aliphatic polyester resin composition containing a specific organic compound, and a molded article thereof.

[0002]

2. Description of the Related Art In recent years, plastic transparent films have been used for electronics, mechatronics, optoelectronics, lasers (optical communication, CD, CD-ROM, LD,
DVD, magneto-optical recording (MO) and the like are also included. ), Liquid crystal, optics, office automation (OA), factory automation, etc., and the use thereof has been expanding dramatically with the rapid development of technology. Specific examples of the application include, for example, applications for films for overhead projectors, films for plate making, tracing films, food wrapping films, agricultural films, and the like. Specific examples of high-performance applications include, for example, transparent conductive films (for example, screen touch panels for computer input), heat ray reflective films, films for liquid crystal displays, polarizing films for liquid crystal displays, and PCBs (printed circuit boards). No. Glass, acrylic (polymethyl methacrylate, PMM
A) In conventional applications where rigid films with low flexibility (flexibility) such as polycarbonate (PC) were used, transparent films excellent in flexibility, moldability, heat resistance, etc. were used. Tend to be required. Some of these alternative demands can be met with polyethylene terephthalate (PET) films.

[Technical Background of Aliphatic Polyesters from the Perspective of Environmental Conservation] Recently, when general-purpose plastics are discarded after use, the amount of garbage increases, and since they are hardly decomposed in the natural environment, they are buried. Even so, plastics that remain semi-permanently in the ground and have been dumped have caused problems such as degrading the landscape and destroying the living environment of marine life. Against this background, recent research and development trends in the technical field of transparent films have focused on improving degradability and heat resistance.

[Technical Background on Aliphatic Polyesters] Aliphatic polyesters are easily hydrolyzed in the presence of water.
It is environmentally friendly because it is decomposed without contaminating the environment after disposal, and when placed in a living body as a medical material, it has little or no effect on the living body after achieving its purpose, and it is decomposed and absorbed in the living body Since it is an excellent biodegradable polymer that is easy on living organisms, it has already attracted attention as a substitute for medical materials and general-purpose resins before the present application.

[0005] The properties of these aliphatic polyesters are various, such as hard and soft, low and high heat resistance, transparent and opaque, but none of them have both heat resistance and transparency. For example, in the case of a molded article of polylactic acid, it can be obtained in an amorphous state by ordinary molding and is transparent, but the heat resistance is low at a Vicat softening point of 60 ° C. Further, there is a problem that when heat treatment is performed to increase crystallinity and heat resistance, the film becomes opaque.

Further, in the case of a molded article of polybutylene succinate, it can be obtained by the usual molding with crystallinity, and the heat resistance is opaque although the Vicat softening point is relatively high at 110 ° C.

[Transparency technology in general-purpose resins] In the technical field related to general-purpose resins, a technique of adding a crystal nucleating agent for the purpose of suppressing the growth of spherulites, imparting transparency, or accelerating the crystallization speed. It has been known. As a specific example, for example, a method of adding a sorbitol derivative to impart transparency to a polypropylene resin (Japanese Patent Publication No.
-12460) or a method of adding a finely divided whole aromatic polyester powder mainly composed of terephthalic acid and resorcinol in order to accelerate the crystallization rate of polyethylene terephthalic acid (JP-A-60-86156). ) And the like.

From these viewpoints, the present inventors have considered that, as a nucleating agent for an aliphatic polyester, a sol beer derivative which is a transparent nucleating agent for a polypropylene resin, a phosphorus-based nucleating agent, talc, an ultrafine particle diameter, etc. (1 to several tens of nm) Injection molding was attempted using silica, calcium lactate, sodium benzoate, or the like, but it was not possible to simultaneously impart transparency and crystallinity to the aliphatic polyester.

[Additives of Aliphatic Polyester] In the technical field related to aliphatic polyesters, for example, the following techniques for adding additives are known.
The fact is that little is known about the technique of adding a nucleating agent for the purpose of suppressing spherulite growth, imparting transparency or accelerating the crystallization rate.

[Japanese Patent Application Laid-Open No. 5-70696]
No. 0696 discloses a plastic container made of a biodegradable plastic such as poly-3-hydroxybutyrate / poly-3-hydroxyvalerate copolymer, polycaprolactone or polylactic acid, and having an average particle diameter of 20 μm.
It is disclosed that 10 to 40% by weight of calcium carbonate and hydrous magnesium silicate (talc) of m or less are mixed. However, in this technique, although the decomposability can be promoted by adding a large amount of an inorganic filler, it is naturally difficult to improve the transparency and heat resistance (crystallinity) of the polymer. It is.

[Tokuhyohei 4-5047731 (WO 90)
/ 01521)] Japanese Patent Publication No. Hei 4-5047731 (W
O 90/01521) discloses a technique for changing the properties of hardness, strength and temperature resistance by adding a filler of an inorganic compound such as silica or kaolinite to a lactide thermoplastic. I have. In the examples, L, DL-lactide copolymer was added as a nucleating agent,
By adding 5% by weight of calcium lactate and blending with a heated roll at 170 ° C for 5 minutes, it has excellent rigidity and strength,
A technique for manufacturing a sheet having a high crystallinity is disclosed. However, it is also disclosed that transparency is significantly reduced in such a technique.

[Tokuhyo 6-504799 (WO 92)
/ 04413)] Japanese Patent Publication No. 6-504799 (W
O 92/04413) discloses a technique in which lactate and benzoate are added as nucleating agents to lactide thermoplastics. In the example, the polylactide copolymer is blended with 1% calcium lactate,
Disclosed is a technique of injection molding with a mold maintained at about 85 ° C. with a residence time of 2 minutes, and annealing at about 110 to 135 ° C. in the mold. In this case, too, it is disclosed that the transparency is significantly reduced.

[0013]

[Problems to be solved by the invention]

[Location of Problem] The present inventors have found that it is difficult to simultaneously develop transparency and crystallinity by a new technique in an aliphatic polyester which is difficult to simultaneously exhibit transparency and crystallinity by the conventional technique. I thought that it was a very significant solution. Conventionally, the person skilled in the art has never recognized the location of such a problem by the present inventors. [Problems to be Solved by the Invention] An object of the present invention is to provide a molded article of an aliphatic polyester resin composition having both transparency and heat resistance (high crystallization).

[0014]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that by adding a specific compound, crystallization can be achieved while maintaining transparency. The present invention has been completed. The present invention is specified by the following items [1] to [7]. The evaluation method of the melting entropy (dimension [cal / K / mol]) is based on the atomic group contribution method.

[1] A method for producing an aliphatic polyester molded article having both transparency and crystallinity by molding an aliphatic polyester resin composition containing a transparent nucleating agent and crystallizing the same during or after molding. The transparent nucleating agent has a melting point or softening point of 80 to 300 ° C .;
A method for producing an aliphatic polyester molded article having both transparency and crystallinity, which is at least one organic compound selected from the group consisting of organic compounds having a melting entropy of 0 to 100 cal / K / mol. .

[2] The “organic compound having a melting point or softening point of 80 to 300 ° C. and having a melting entropy of 10 to 100 cal / K / mol” is an organic compound having at least one amide bond. , [1], the method for producing an aliphatic polyester molded article having both transparency and crystallinity.

[3] The “organic compound having a melting point or softening point of 80 to 300 ° C. and a melting entropy of 10 to 100 cal / K / mol” includes an ester bond, a carboxylate, a carboxyl group, and The method for producing an aliphatic polyester molded article having both transparency and crystallinity according to [1], which is an organic compound having at least one selected from the group consisting of hydroxyl groups.

[4] The method for producing an aliphatic polyester molded article having both transparency and crystallinity according to any one of [1] to [4], wherein the "aliphatic polyester" is a lactic acid-based polymer.

[5] An aliphatic polyester molded article having both transparency and crystallinity, obtained by the production method according to any one of [1] to [4].

[6] At least one organic compound selected from the group consisting of organic compounds having a melting point or softening point of 80 to 300 ° C. and a melting entropy of 10 to 100 cal / K / mol, A method of using as a transparent nucleating agent for an aromatic polyester resin composition.

[7] The “organic compound having a melting point or softening point of 80 to 300 ° C. and having a melting entropy of 10 to 100 cal / K / mol” is an organic compound having at least one amide bond. , [6].

[8] The “organic compound having a melting point or softening point of 80 to 300 ° C. and a melting entropy of 10 to 100 cal / K / mol” includes an ester bond, a carboxylate, a carboxyl group, The method according to [6], wherein the organic compound has at least one selected from the group consisting of a hydroxyl group.

[9] The method according to any one of [6] to [8], wherein the “aliphatic polyester” is a lactic acid-based polymer.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [Aliphatic polyester] In the present invention, the aliphatic polyester is a homopolymer (eg, polylactic acid, polyglycolic acid, polycaproic acid, etc.) and a copolymer (eg, a copolymer of lactic acid and glycolic acid, Homopolymers of aliphatic polyhydric alcohols and aliphatic polycarboxylic acids (eg, polybutylene succinate, polyethylene adipate, etc.) and copolymers (eg, copolymers of butanediol with succinic acid and adipic acid) Copolymers of ethylene glycol and butanediol and succinic acid, etc.), copolymers of aliphatic hydroxycarboxylic acids and aliphatic polyhydric alcohols and aliphatic polycarboxylic acids (eg, block copolymers of polylactic acid and polybutylene succinate), and It includes a mixture of these. In the case of a mixture, a compatibilizer may be contained. When the aliphatic polyester is a copolymer, the mode of arrangement of the copolymer may be any mode such as a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer. Furthermore, these may be at least partially cross-linked with a cross-linking agent such as xylylene diisocyanate, polyvalent isocyanate such as 2,4-tolylene diisocyanate or polysaccharide such as cellulose, acetyl cellulose or ethyl cellulose. Well, at least partly, linear, annular,
Any structure such as a branched shape, a star shape, and a three-dimensional network structure may be employed, and there is no limitation.

In the aliphatic polyester of the present invention, polylactic acid, particularly poly-L-lactic acid, polycaproic acid, particularly poly-ε-caproic acid, a block copolymer of polylactic acid and poly-6-hydroxycaproic acid, particularly poly-L Block copolymers of monolactic acid and poly-6-hydroxycaptoic acid, polybutylene succinate, block copolymers of polylactic acid and polybutylene succinate, particularly block copolymers of poly-L monolactic acid and polybutylene succinate are preferred.

[Aliphatic hydroxycarboxylic acid] Specific examples of the aliphatic hydroxycarboxylic acid constituting the aliphatic polyester in the present invention include, for example, glycolic acid,
Lactic acid, 3-hydroxy drank acid, 4-hydroxy drank acid, 4-
Hydroxyvaleric acid, 5-hydroxyvaleric lactic acid, 6-hydroxycaproic acid and the like can be mentioned. These may be one kind or a mixture of two or more kinds. When the aliphatic hydroxycarboxylic acid has an asymmetric carbon, it may be an L-form, a D-form, or a mixture thereof, that is, a racemic form.

[Aliphatic polycarboxylic acid and its anhydride]
Specific examples of the aliphatic polycarboxylic acid constituting the aliphatic polyester in the present invention include, for example, oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Examples thereof include aliphatic dicarboxylic acids such as undecanoic acid and dodecane diacid, and anhydrides thereof. These may be one kind or a mixture of two or more kinds.

[Aliphatic Polyhydric Alcohol] Specific examples of the aliphatic polyhydric alcohol constituting the aliphatic polyester in the present invention include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 3-butanediol, 1,4-butanediol, 3-methyl-1,5
-Pentanediol, 1,6-hexanediol, l,
Examples include 9-nonanediol, neopentyl glycol, tetramethylene glycol, 1,4-cyclohexanedimethanol, and the like. These may be one kind or a mixture of two or more kinds.

[Polysaccharides] Specific examples of polysaccharides include, for example, cellulose, cellulose nitrate, cellulose acetate, methylcellulose, ethylcellulose, celluloid, viscose rayon, regenerated cellulose, cellophane, cupra, cuprammonium rayon, cuprophan, Bemberg , Hemicellulose, starch, amylopectin, dextrin, dextran, glycogen, pectin, chitin, chitosan, gum arabic, guar gum, locust bean gum, acacia gum, and the like, and derivatives thereof, with acetyl cellulose and ethyl cellulose being particularly preferred. Used for These may be one kind or a mixture of two or more kinds.

[Molecular Weight of Aliphatic Polyester] The molecular weight of the aliphatic polyester used in the present invention may be substantially sufficient in mechanical properties when it is used for a target application, for example, a molded article such as a packaging material and a container. If shown,
The molecular weight is not particularly limited. In general, the molecular weight of the aliphatic polyester is preferably 1 to 5,000,000, more preferably 3 to 3,000,000, more preferably 5 to 2,000,000, still more preferably 7 to 1,000,000, as weight average molecular weight, ~ 500,000 is most preferred. In general, when the weight average molecular weight is smaller than 10,000, mechanical properties are not sufficient, and when the molecular weight is larger than 5,000,000, handling may be difficult or uneconomical. The weight average molecular weight and the molecular weight distribution of the aliphatic polyester used in the present invention, in the production method, the type of solvent, the type and amount of the catalyst, the reaction temperature, the reaction time, the method of embedding the solvent distilled by azeotropic, The desired system can be controlled by appropriately selecting reaction conditions such as the degree of dehydration of the solvent in the reaction system.

[Method for Producing Aliphatic Polyester] The method for producing the polyester of the present invention is not particularly limited. For example, a specific example of a method for producing polylactic acid and an aliphatic polyester having lactic acid as a structural unit is described in JP-A-6-6553.
A method as shown in Production Example 2 described below with reference to the method disclosed in No. 60 is available. That is, it is a direct dehydration condensation method in which lactic acid and / or a hydroxycarboxylic acid other than lactic acid, or an aliphatic diol and an aliphatic dicarboxylic acid are directly dehydrated and condensed in the presence of an organic solvent and a catalyst.

As another reference example of a method for producing an aliphatic polyester having lactic acid as a structural unit, see, for example,
Methods described in Production Examples 3 to 6 described below with reference to the method disclosed in US Pat. That is, this is a method in which a homopolymer of at least two kinds of aliphatic polyesters is copolymerized and transesterified in the presence of a polymerization catalyst. As another specific example of the method for producing polylactic acid, for example, a method as shown in Production Example 1 described below with reference to the method disclosed in US Pat. No. 2,703,316 is exemplified. That is, it is an indirect polymerization method in which lactic acid and / or a hydroxycarboxylic acid other than lactic acid is once dehydrated into a cyclic dimer, and then subjected to ring-opening polymerization.

[Transparent Nucleating Agent] In the technical field of resin,
The term “nucleating agent” or “crystal nucleating agent” includes additives having a function of suppressing spherulite growth, imparting transparency, and promoting a crystallization rate. In the specification of the present application,
The term "nucleating agent" or "crystal nucleating agent", for example, suppresses the growth of crystal size such as spherulite by increasing the crystallization rate, and substantially reduces the crystal size of spherulite or the like more than the wavelength of visible light. Additives that have the function of exhibiting high transparency even at a high degree of crystallinity by maintaining an extremely small size are included.

In the specification of the present application, the term “nucleating agent” or “crystal nucleating agent” means, for example,
When added to a system with relatively small number of crystals and relatively large size, it is converted to a system with relatively large number and relatively small size of crystals. Additives.

[Melting Entropy] The value of the melting entropy is “PROPERTIES OF POLYMERS”.
(Third, completely raised
edition), D.C. W. VAN KREVEREN
Ed., ISBN-0-444-88160-3, Else
via Science Publishers, 1
990 ”, page 122, based on the atomic group contribution method. All the descriptions are incorporated as a part of the disclosure of the specification of the present application by explicitly citing the cited documents and the cited range, and by referring to the explicitly cited ranges, the matters or disclosures described in the specification of the present application are all Matters or disclosures that can be directly and uniquely derived by the trader. The melting entropy is 10 cal / K / mol to 100 cal / K when determined by the group contribution method.
/ Mol range. The contribution of the meta-substituted phenylene group is assumed to be the same as the para-substitution. The urethane group contributes 1.5 times the amide group. In addition, only when the contribution of the group is not given and the melting entropy cannot be determined by the group contribution method,
This can be substituted by estimation from measured values or estimation from theoretical calculation by computer.

[Organic compound having a melting point or softening point of 80 to 300 ° C. and a melting entropy of 10 to 100 cal / K / mol] The transparent nucleating agent used in the present invention has a melting point of 80 to 300 ° C. Or having a softening point, and
It is not particularly limited as long as it is an organic compound having a melting entropy of 10 to 100 cal / K / mol. The melting point or softening point of the transparent nucleating agent used in the present invention is 80 to 300.
° C, preferably 80-250 ° C, more preferably 80-250 ° C.
The temperature is 200 ° C, more preferably 80 to 175 ° C. The melting entropy of the transparent nucleating agent used in the present invention is 10 to 10.
100 [cal / K / mol], preferably 20 to 90
[Cal / K / mol], more preferably 25 to 85
[Cal / K / mol].

The transparent nucleating agent used in the present invention is 80 to 30.
It has a melting point or softening point of 0 ° C., and 10-100 ca
Specific examples of the organic compound having a melting entropy of 1 / K / mol include, for example, carboxylic acid amide, carboxylic acid ester, carboxylic acid, carboxylic acid salt, alcohol, and the like, with carboxylic acid amide being particularly preferred.

The transparent nucleating agent used in the present invention is 80 to 30.
It has a melting point or softening point of 0 ° C., and 10-100 ca
Specific examples of the organic compound having a melting entropy of 1 / K / mol include, for example, aliphatic carboxylic acid amide,
Examples thereof include an aliphatic carboxylic acid ester, an aliphatic carboxylic acid, an aliphatic carboxylic acid salt, and an aliphatic alcohol, and an aliphatic carboxylic acid amide is particularly preferable.

The transparent nucleating agent used in the present invention is 80 to 30.
It has a melting point or softening point of 0 ° C., and 10-100 ca
Specific examples of the organic compound having a melting entropy of 1 / K / mol include, for example, aromatic carboxylic acid amide,
Examples thereof include an aromatic carboxylic acid ester, an aromatic carboxylic acid, an aromatic carboxylate, and an aromatic alcohol, and an aromatic carboxylic acid amide is particularly preferable.

The transparent nucleating agent used in the present invention is 80 to 30.
It has a melting point or softening point of 0 ° C., and 10-100 ca
Specific examples of the organic compound having a melting entropy of 1 / K / mol include, for example, alicyclic carboxylic acid amide,
Alicyclic carboxylic esters, alicyclic carboxylic acids, alicyclic carboxylate salts, alicyclic alcohols and the like can be mentioned, with alicyclic carboxylic amides being particularly preferred.

[Aliphatic carboxylic acid amide] The above-mentioned aliphatic carboxylic acid amide has a melting point or a softening point of 80 to 80.
It is in the range of 300 ° C. and has a melting entropy of 10 to 10
There is no particular limitation on the aliphatic carboxylic acid amide in the range of 0 cal / K / mol. Aliphatic carboxylic acid amides include "fatty acid amides" described on page 389, right column to page 391, left column of "10889 Chemical Products (1989, Chemical Daily, Inc., Nihonbashi-hama-cho, Chuo-ku, Tokyo)". . All the descriptions are incorporated as a part of the disclosure of the specification of the present application by explicitly citing the cited documents and the cited range, and by referring to the explicitly cited ranges, the matters or disclosures described in the specification of the present application are all Matters or disclosures that can be directly and uniquely derived by the trader. The aliphatic carboxylic acid amide in the present invention is a compound containing at least one structure in which nitrogen is bonded to carbonyl carbon. Specifically, it includes a bond usually called an amide bond, and also includes a bond usually called a urea bond. A hydrogen atom or an aliphatic group is bonded to each of the carbonyl carbon and the nitrogen atom bonded to the carbonyl carbon. Specifically, the aliphatic group to be bonded is not only an aliphatic group in a narrow sense, but also an aromatic group, a group obtained by combining them, or a group in which these are bonded by oxygen, nitrogen, sulfur, silicon, phosphorus, or the like. It also includes a group consisting of residues having a structure, and more specifically,
For example, a group consisting of a residue having a structure in which a hydroxyl group, an alkyl group, a cycloalkyl group, an allyl group, an alkoxyl group, a cycloalkoxyl group, an allyloxyl group, a halogen (F, Cl, Br, etc.) group is substituted is included. I do. By appropriately selecting these substituents, the effect as a nucleating agent can be controlled, whereby various characteristics (heat resistance) of a resin composition comprising an aliphatic polyester including a lactic acid-based polymer according to the present invention can be controlled. , Strength characteristics, etc.) can also be controlled.

Specific examples of the aliphatic carboxylic acid amide include, for example, lauric amide, palmitic amide,
Stearic acid amide, erucic acid amide, behenic acid amide, N-stearyl stearic acid amide, methylol stearic acid amide, methylol behenic acid amide, dimethylitol oil amide, dimethyl lauric acid amide, dimethyl stearic acid amide No. Other ethylene bis oleic acid amide, ethylene bis stearic acid amide, ethylene bis lauric acid amide, hexamethylene bis oleic acid amide, butylene bis stearic acid amide, m-xylylene bis stearic acid amide, m-xylylene bis-12 hydroxy stearic acid amide , N,
N-butyl-N'stearyl such as N'-dioleyladipamide, N, N'-distearyladipamide, N, N'-distearylisophthalamide, N, N'-distearylterephthalamide Urea, N-propyl-N ′ stearyl urea, N-allyl-N ′ stearyl urea, N-stearyl-N ′ stearyl urea and the like can be mentioned. In particular, palmitic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, ethylenebisoleic acid amide, ethylenebislauric acid amide, N
-Stearyl stearamide, m-xylylene bis stearamide, and m-xylylene bis-12 hydroxystearate are preferably used. These may be one kind or a mixture of two or more kinds.

[Addition amount of aliphatic carboxylic acid amide] The addition amount of the aliphatic carboxylic acid amide is 0.001 to 1 with respect to the aliphatic polyester including the lactic acid-based polymer.
0% by weight, preferably 0.01 to 7.0% by weight, more preferably 0.03 to 5.00%, and most preferably 0.05 to 3.00% by weight. 0.001% by weight
If it is smaller, the effect as a nucleating agent may be insufficient. On the other hand, if it is more than 10% by weight, not only the effect as a further nucleating agent will not be obtained, but also the appearance and physical properties may change. May be.

[Inorganic Additive] As long as the transparency of the molded article is not impaired,
In order to improve various physical properties such as an improvement in crystallization speed, an improvement in heat resistance, an improvement in mechanical properties, and an improvement in blocking resistance, an inorganic additive may be added. Specific examples of the inorganic additive include, for example, talc, kaolinite, SiO2, and clay. However, it is necessary to appropriately select conditions (addition amount, particle size) so as not to impair the transparency of the molded article. is there. In order to maintain the transparency of the molded article, it is generally recommended to select a particle size substantially smaller than the wavelength of visible light. More specifically, when the purpose is to improve the physical properties of blocking resistance, for example, the particle size is 1 to 50
nm (7) SiO2 or the like is preferably used without impairing the transparency. In the production method of the present invention, when the purpose is to further improve the crystallization rate during molding such as crystallization in a mold during molding or crystallization by heat treatment of the formed compact, the SiO2 component is used. A crystalline inorganic substance containing 10% by weight or more is preferable. Specifically, talc TM-30
(Manufactured by Fuji Talc), kaolin JP-100 (manufactured by Tsuchiya Kaolin), NN kaolin clay (manufactured by Tsuchiya Kaolin), kaolinite ASP-170 (manufactured by Fuji Talc), kaolin UW (manufactured by Engelhard), talc R
F (manufactured by Fuji Talc) and the like. In this case, a material having a small particle size and being well dispersed without being aggregated when melt-kneaded with a resin is suitably used.

The amount of the inorganic additive is preferably such that the transparency of the molded article is not extremely impaired, and is preferably 30% by weight or less, more preferably 20% by weight or less, based on 100 parts by weight of the aliphatic polyester. It is preferably at most 10% by weight, more preferably at most 5% by weight, most preferably at most 1% by weight.

[Plasticizer] A plasticizer can be used in combination with the molded article produced by the production method of the present invention in order to increase the crystallization speed. The plasticizer used for such purpose is not particularly limited as long as it has a function of increasing the crystallization rate.For example, even if it is an aromatic compound such as a phthalic acid compound, an epoxy compound, an ester It may be an aliphatic compound such as a system compound. Preferred specific examples of the plasticizer include aliphatic compounds such as tributyl acetylcitrate, diisodecyl adipate, dibutyl sebacate, and triacetin. The amount of the plasticizer added depends on the type of the additive, but is preferably an amount that does not extremely impair the transparency of the aliphatic polyester.
0% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less,
Most preferably, 1% by weight or less is suitable. The molded article produced by the production method of the present invention may further include various elastomers (SBR, N) as long as the transparency of the molded article is not impaired.
BR, SBS type ternary block copolymer, thermoplastic elastomer, etc.) and additives (plasticizer, pigment, stabilizer, antistatic agent, ultraviolet absorber, antioxidant, flame retardant, release agent, lubricant, dye) , An antibacterial agent), a filler (impact-resistant core / shell type particles, impact modifier, etc.), and a pigment (metallic pigment, pearl pigment) can be appropriately used according to the purpose and application.

[Molding Method] <Mixing / Kneading / Kneading> In the present invention, an aliphatic polyester and an organic compound having a melting point or softening point of 80 to 300 ° C. and a melting entropy of 10 to 100 cal / K / mol are used. A method for producing an aliphatic polyester composition by mixing, kneading, and kneading at least one selected transparent nucleating agent is a known and publicly known kneading technique, such as a Henschel mixer or a ribbon blender. Or kneading while melting the polymer using an extruder or the like.

<Molding> A method for producing a molded article having both transparency and crystallinity, which is the object of the present invention, will be described below. The present invention is a method for producing a molded article having both transparency and crystallinity by crystallizing the above-mentioned aliphatic polyester resin composition at the time of molding or after molding. Examples of the molding method include ordinary methods such as injection molding, extrusion molding, blow molding, inflation molding, profile extrusion molding, injection blow molding, vacuum pressure molding, and spinning.In the resin composition shown in the present invention, It can be applied to any molding method, and there is no limitation. For example, in the case of a lactic acid-based polymer, an amorphous molded body can be obtained by a usual molding method, and in this case, it is necessary to crystallize by some method (for example, heat treatment). As a specific example of crystallizing the aliphatic polyester resin composition at the time of molding or after molding, for example, a method of filling a melt of the composition into a mold at the time of molding, crystallizing the same in the mold, and A method of heat-treating an amorphous compact of the composition can be used.

<Embodiment of Method for Producing a Molded Body Having Both Transparency and Crystallinity> The following is a description of the method for molding a molded body according to the present invention, which can simultaneously impart transparency and crystallinity to a molded body. An embodiment will be described. In the present invention, the fact that the aliphatic polyester molded article has transparency means that the thickness is l.
mm means that when the newspaper is overlaid on the molded article, the transparency of the newspaper is such that letters of the newspaper can be recognized through the molded article. The molded article having a thickness of 1 mm has a haze of 30% or less. Means that In the present invention, that the aliphatic polyester molded article is crystalline means that the crystallinity measured by the X-ray diffraction method is 10% or more. According to the production method of the present invention, an aliphatic polyester molded article having both crystallinity (heat resistance) and transparency having a crystallinity of 10% or more and a haze of 30% or less at a thickness of 1 mm is obtained. According to the production method of the present invention, even if the crystallinity is 30% or more, the haze is 30% or less at a thickness of 1 mm, and the aliphatic (having both crystallinity (heat resistance) and transparency of 15% or less) is 1 mm in thickness. A polyester molding is obtained.

The transparent, crystalline (heat-resistant) and decomposable aliphatic polyester molded articles of the present invention can be obtained by injection molding, film, bag, tube, sheet, cup, Includes pottle, tray, thread, etc.
There are no restrictions on the shape, size, thickness, design, etc. Specifically, the molded article of the present invention is a food packaging bag, a container or tray for food such as tableware, forks and spoons,
Bottles for dairy products, soft drinks and alcoholic beverages, wrap films, cosmetic containers, garbage bags, caps, tents, waterproof sheets, (adhesive) tapes, air mats, containers for bleach,
Bottles for liquid detergents, containers and packaging materials for medical instruments and medical materials, containers and packaging materials for pharmaceuticals, fishing lines, fishnets, containers and packaging materials and capsules for agricultural supplies, containers and packaging materials and capsules for fertilizers It can be used for containers and packaging materials for seedlings, capsules, films for agricultural and horticultural use, films for product packaging, films for overhead projectors, heat ray reflective films, films for liquid crystal displays, and the like.

In addition, the film or sheet obtained by the method of the present invention is laminated with a sheet of another material such as paper or another polymer by laminating or laminating with an adhesive or heat fusion, etc. It can also be a body. In particular, conventionally, an amorphous film of an aliphatic polyester having excellent transparency such as a copolymer having polylactic acid or a polylactic acid block and a polybutylene succinate block, for example, when heat-laminated to paper or the like However, there has been a problem that the material is crystallized and becomes opaque due to heat during lamination. Therefore, in applications where transparency is required, heat treatment conditions during thermal lamination are limited, or a lamination method using an adhesive is preferably used.Moreover, in applications where transparency and heat resistance are required, The resin composition could not be used. However, when those resin compositions containing the transparent nucleating agent of the present invention are used, for example, a transparent amorphous film is heat-laminated on paper or the like as it is, bonded to paper or the like, and crystallized of the composition. May be performed simultaneously. Further, the laminated body once subjected to thermal lamination may be further heat-treated to be crystallized.
Under any conditions, maintain its transparency, and furthermore,
A laminate having heat resistance can be obtained.

[0052]

[Examples] Production examples, examples and comparative examples are shown below.
The present invention will be described in detail. Note that descriptions of synthesis examples, examples, comparative examples, aspects and the like in the specification of the present application are descriptions for assisting understanding of the contents of the present invention, and the description narrows the technical scope of the present invention. It is not of a nature to be interpreted.

A. Production Examples Production methods of the aliphatic polyester used in Examples and Comparative Examples are shown below. All parts in the text are based on weight. The average molecular weight (weight average molecular weight Mw) of the polymer was measured by gel permeation chromatography using polystyrene as a standard under the following conditions. Apparatus: Shimadzu LC-IOAD Detector: Shimadzu RID-6A Column: Hitachi Chemical GL-S350DT-5, GL-
S370DT-5 Solvent: chloroform Concentration: 1%

[Production Example 1] Production of polymer A (poly L-lactide) 100 parts of L-lactide and stannous octoate 0.1 part.
01 parts and 0.03 parts of lauryl alcohol were sealed in a thick cylindrical stainless steel polymerization vessel equipped with a stirrer, degassed under vacuum for 2 hours, and then replaced with nitrogen gas. The mixture was heated at 200 ° C. for 3 hours with stirring under a nitrogen atmosphere. While maintaining the temperature as it was, the air was gradually degassed by a vacuum pump through an exhaust pipe and a glass receiver, and the pressure inside the reaction vessel was reduced to 3 mmHg. One hour after the start of degassing,
Since the distilling of the monomer and low molecular weight volatile components disappeared, the inside of the container was replaced with nitrogen, and the monomer was drawn out from the lower part of the container in a string form and pelletized to obtain a polymer A of L-lactide. The weight average molecular weight Mw of this polymer was 136,000.

[Production Example 2] Production of polymer B (poly-L-lactic acid) 10 kg of 90% L-lactic acid was placed at 150 ° C / 50 in a 100-liter reactor equipped with a Dien-Stark trap.
After distilling water while stirring at 3 mmHg for 3 hours, 6.2 g of tin powder was added and the mixture was stirred at 150 ° C./30 mmHg for another 2 hours to oligomerize. This oligomer has tin powder 2
8.8 g and 21.1 kg of diphenyl ether were added, and 1
An azeotropic dehydration reaction was performed at 50 ° C./35 mmHg, and the distilled water and the solvent were separated by a water separator, and only the solvent was returned to the reactor. Two hours later, the organic solvent to be returned to the reactor was passed through a column packed with 46 kg of molecular sieve 3A, and then returned to the reactor. The reaction was carried out at 150 ° C./35 mmHg for 40 hours, and polylactic acid having an average molecular weight of 146,000 was obtained. A solution was obtained. To this solution was added 44 kg of dehydrated diphenyl ether, diluted and cooled to 40 ° C., and the precipitated crystals were filtered, washed with 10 kg of n-hexane three times, and washed at 60 ° C.
/ 50 mmHg. This powder is mixed with 0.5N-HC
112 kg and ethanol 12 kg were added, and the mixture was stirred at 35 ° C. for 1 hour, filtered, and dried at 60 ° C./50 mmHg to obtain 6.1 kg of polylactic acid powder (yield: 85%). This powder was melted and pelletized by an extruder to obtain polymer B of L-lactic acid. The weight average molecular weight Mw of the polymer B
Was 145,000.

[Production Example 3] Production of polymer C (polybutylene succinate) 50.5 g of 1,4-butanediol and 66.5 of succinic acid
g to diphenyl ether 293. Og, metal tin 2.02
g was added thereto, and the mixture was heated and stirred at 130 ° C./140 mmHg for 7 hours while distilling water out of the system to form an oligomer. to this,
Attach Dean-Stark trap, 140 ° C
After azeotropic dehydration at 30 mmHg for 8 hours, a tube filled with 40 g of molecular sieve 3A was attached, and the distilled solvent was returned to the reactor through the molecular sieve tube and stirred at 130 ° C./17 mmHg for 49 hours. did. The reaction mass was dissolved in 600 ml of chloroform, added to 4 liters of acetone and reprecipitated, and then a solution of HCl in isopropyl alcohol (hereinafter abbreviated as IPA) (H
(Cl concentration: 0.7 wt%) for 0.5 hour (three times), washed with IPA, and dried under reduced pressure at 60 ° C. for 6 hours to obtain polybutylene succinate (hereinafter abbreviated as PSB). The weight average molecular weight Mw of this polymer is 1
It was 18,000.

[Production Example 4] Production of copolymer D (butylene succinate / lactic acid copolymer) 80.0% of polybutylene succinate obtained in Production Example 3
g, polylactic acid 12 obtained by the same method as in Production Example 2.
0.0 g (weight average molecular weight Mw is 2,000,000), 800 g of diphenyl ether and 0.7 g of metal tin were mixed, and
The dehydration condensation reaction was performed at 30 ° C./17 mmHg for 20 hours. After completion of the reaction, post-treatment was carried out in the same manner as in Production Example 2 to obtain a copolymer C of polybutylene succinate and polylactic acid (weight average molecular weight Mw: 14,000).

[Production Example 5] Production of copolymer E (butylene succinate / lactic acid copolymer) 40.0 g of polybutylene succinate (weight average molecular weight Mw is 118,000) and 160.0 g of polylactic acid (weight average molecular weight) The same method as in Production Example 4 was carried out except that Mw was 500000). As a result, a copolymer E of polybutylene succinate and polylactic acid (weight average molecular weight Mw was 13.6)
10,000).

[Production Example 6] Production of copolymer F (butylene succinate / lactic acid copolymer) 20.0 g of polybutylene succinate (weight average molecular weight Mw is 118,000) and 180.0 g of polylactic acid (weight average molecular weight) Except for using Mw of 100,000), the same method as in Production Example 4 was carried out. As a result, a copolymer F of polybutylene succinate and polylactic acid (weight average molecular weight: 142,000) was used.
I got

[Production Example 7] Production of copolymer G (caproic acid / lactic acid copolymer) The result of performing a reaction in the same manner as in Production Example 2 except that 6-hydroxycaproic acid was used instead of polylactic acid. And polycaproic acid (weight average molecular weight Mw: 150,000). Next, using 20.0 g of the obtained polycaproic acid and 180.0 g of polylactic acid (weight average molecular weight Mw is 100,000), the same procedure as in Production Example 4 was carried out to obtain a copolymer G weight average of polycaproic acid and polylactic acid. The molecular weight Mw is 15.3
10,000).

B. Examples Using the lactic acid-based polymer and polybutylene succinate obtained in Production Examples 1 to 7, a method and examples for producing a polylactic acid-based resin composition according to the present invention will be described.

[Evaluation of Physical Properties] The conditions for evaluating the physical properties are as follows. Crystallinity X-ray diffractometer (Rig 1500, manufactured by Rigaku Corporation)
(Mold), the test piece after molding was measured, and the ratio of the crystal peak area of the obtained chart to the total area was determined. Transparency (Haze) According to JIS K-6714, Haze M manufactured by Tokyo Denshoku
The measurement was carried out using an eter. Heat resistance [Vicat softening temperature (ASTM-D152
5)] A test piece after molding was measured under a load of 1 kgf.

Example 1 100 parts by weight of the polylactic acid obtained in Production Example 1 and 1% by weight of ethylenebislauric amide as a transparent nucleating agent were thoroughly mixed with a Henschel mixer. Pellets were formed at 210 ° C. The pellets were transferred to JSW JSW
-75 injection molding machine, cylinder set temperature 180-200
Melting under the condition of ° C, filling in a mold at the set temperature of 30 ° C,
The cooling time was 30 seconds to obtain a transparent and flat plate-shaped molded article having a thickness of 1.0 mm. The transparency (haze) of this flat plate was 2%, the crystallinity was 0%, and the Vicat softening point was 59 ° C. This flat plate was heat-treated in a dryer at 100 ° C./30 min.
The transparency (haze) of the obtained flat plate was 6%, and the crystallinity was 42.
%, Vicat softening point was 150 ° C. Table 1 shows the results.
It is shown in [Table 1].

[Examples 2 to 11] The same procedures as in Example 1 were carried out except that the types and amounts of the polymer and the transparent nucleating agent were changed as shown in Table 1 [Table 1]. The transparency (haze), crystallinity, and Vicat softening point of the flat plate were measured. The results are shown in Table 1 [Table 1].

Comparative Example 1 The same procedure as in Example 1 was carried out except that ethylenebislauric amide as a transparent nucleating agent was omitted. The haze value of the obtained plate was 2%, the crystallinity was 0%,
The Vicat softening point was 59 ° C. The transparency (haze) when this plate was heat-treated in a dryer at 100 ° C./20 min was 83%, the crystallinity was 45%, and the Vicat softening point was 1
It was 50 ° C. The results are shown in Table 2 [Table 2].

[Comparative Examples 2 to 7] Table 2 [Table 2] shows the types and amounts of the polymer and the transparent nucleating agent and the heat treatment conditions in the dryer.
The transparency was measured in the same manner as in Example 1 except that the transparency (haze), the crystallinity, and the Vicat softening point of each obtained flat plate were measured. The results are shown in Table 2 [Table 2].
Shown in

[How to read Table 1] The way to read Table 1 is as follows. (1) Polymer The polymer or copolymer produced in Production Examples 1 to 6. Homopolymer: A, B, C Copolymer: D, E, F, G (2) Type of additive A: Ethylenebislauric amide Melting point 157 ° C Melting entropy 57.3 cal /
K / mol (Slipax L (trade name), (C11H23C
ONH) 2 (CH 2) 2, Nippon Kasei) B: erucamide Melting point 82 ° C. Melting entropy 45.2 cal / K
/ Mol (NEUTRON-S (trade name), C21H41C
ONH2, Nippon Seika) C: palmitic amide Melting point 100 ° C Melting entropy 35.8 cal /
K / mol (Diamid KP (trade name), C15H31C
ONH2, Nippon Kasei) D: m-xylylenebisstearic acid amide Melting point 123 ° C. Melting entropy 82.0 cal /
K / mol (Slipax PXS (trade name), [C17H
(35CONHCH2] 2 (C6H4), Nippon Kasei) (3) Additive amount of additive It is the weight% of the additive weight based on the polymer weight.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

According to the present invention, a resin composition comprising an aliphatic polyester such as a lactic acid-based polymer having both high transparency and high crystallinity (high heat resistance) can be provided. According to the present invention, a resin composition comprising an aliphatic polyester including a lactic acid-based polymer has high transparency (for example, a haze value of 10% or less) and high crystallinity (for example, a crystallinity of 30% or more). Can be given at the same time.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takayuki Watanabe 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside of Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Yasuhiro Kitahara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Incorporated (72) Inventor Hisashi Aihara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Sunil Christoph Murti 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. In-house (72) Inventor Kazuhiko Suzuki 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Masanobu Amioka 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (9)

[Claims] 1. A method for producing an aliphatic polyester molded article having both transparency and crystallinity by molding an aliphatic polyester resin composition containing a transparent nucleating agent and crystallizing at the time of molding or after molding. The transparent nucleating agent is 80
A melting point or softening point of ~ 300 ° C, and 10 ~ 10
A method for producing an aliphatic polyester molded article having both transparency and crystallinity, which is at least one organic compound selected from the group consisting of organic compounds having a melting entropy of 0 cal / K / mol. 2. The “organic compound having a melting point or softening point of 80 to 300 ° C. and having a melting entropy of 10 to 100 cal / K / mol” is an organic compound having at least one amide bond. The method for producing an aliphatic polyester molded article having both transparency and crystallinity according to claim 1. 3. The “organic compound having a melting point or softening point of 80 to 300 ° C. and a melting entropy of 10 to 100 cal / K / mol” comprises an ester bond, a carboxylate and a hydroxyl group. The method for producing an aliphatic polyester molded article having both transparency and crystallinity according to claim 1, which is an organic compound having at least one at least one selected from the group. 4. The process for producing an aliphatic polyester molded article having both transparency and crystallinity according to claim 1, wherein the “aliphatic polyester” is a lactic acid-based polymer. 5. An aliphatic polyester molded article having both transparency and crystallinity, obtained by the production method according to claim 1. 6. An at least one organic compound selected from the group consisting of organic compounds having a melting point or softening point of 80 to 300 ° C. and a melting entropy of 10 to 100 cal / K / mol, A method of using the polyester resin composition as a transparent nucleating agent. 7. The “organic compound having a melting point or softening point of 80 to 300 ° C. and having a melting entropy of 10 to 100 cal / K / mol” is an organic compound having at least one amide bond. A method according to claim 6. 8. The “organic compound having a melting point or softening point of 80 to 300 ° C. and a melting entropy of 10 to 100 cal / K / mol” comprises an ester bond, a carboxylate, and a hydroxyl group. The method according to claim 6, wherein the organic compound has at least one selected from the group. 9. The method according to claim 6, wherein the “aliphatic polyester” is a lactic acid-based polymer.