JPH1160405A - Biodegradable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a biodegradable resin composition containing a biologically active substance in a profitable amount, having a biologically active function imparted to thereto without deteriorating the characteristics of a base polymer by including a migration-accelerating agent, the aliphatic polyester and the biologically active substance. SOLUTION: This biodegradable resin composition comprises (A) 5-50 wt.% of a migration-accelerating agent such as triacetin, tributyl acetylcitrate, triethylene glycol diacetate or polyethylene glycol, (B) 94.99-40 wt.% of an aliphatic polyester obtained by polymerizing at least one kind of substance selected from (i) aliphatic hydroxycarboxylic acids, (ii) aliphatic hydroxycarboxylic acid cyclic esters, (iii) aliphatic polyhydric alcohols and aliphatic polybasic acids, and (iv) two kinds of monomers selected from the group consisting of the components i-iii and/or the oligomers and/or polymers of the monomers, and (C) 0.01-10 wt. % of a biologically active substance such as an insecticide, an antibiotic, an antibacterial agent, an antifungal agent or a repelling agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an aliphatic polyester and a biologically active substance such as an insecticide, an antibacterial agent and a fungicide.
The present invention relates to a resin composition comprising an aliphatic polyester having properties such as insecticidal, antibacterial, and antifungal properties and decomposing in an environment such as water and compost, and a molded product thereof.

[0002]

2. Description of the Related Art Recently, general-purpose plastics increase the amount of garbage when discarded after use, and are hardly decomposed in the natural environment. In addition, abandoned plastics cause problems such as spoiling the landscape and destroying the living environment of marine life. On the other hand, as polymers having thermoplasticity and degradability, polyhydroxycarboxylic acids such as polylactic acid, and aliphatic polyhydric alcohols such as polybutylene succinate and aliphatic polycarboxylic acids derived from aliphatic polycarboxylic acids. Polyester and the like have been developed. These polymers degrade 100% within the animal's body within months to a year and, when placed in soil or seawater, begin to degrade in a few weeks in a humid environment, about one to several years. In addition, the decomposition products have the property of becoming harmless to the human body and become lactic acid, carbon dioxide, and water, and are thus attracting attention as substitutes for medical materials and general-purpose resins.

[0003] On the other hand, in order to impart antibacterial properties and antifungal properties to plastic molded articles, it is also practiced to directly knead a bioactive substance into plastics such as polyethylene to have such a function. JP-A-8-92006 discloses a biodegradable resin molded product having biodegradability, obtained by kneading a biodegradable resin with a bioactive substance such as an antibacterial agent and the biodegradable resin. . In this technique, a desired function is obtained by a method in which a bioactive substance is impregnated or adsorbed on porous particles or powder and then kneaded with a biodegradable resin. However, in order to impart bioactivity only by kneading the biodegradable resin with the bioactive substance, it is necessary to incorporate a considerable amount of the bioactive substance into the resin, which is not always economical. As described above, the resin composition containing particles and powder may impair the basic physical properties of the resin such as transparency, flexibility, strength, gas permeability, and the like, and a molded product (for example, a molded container, a film) , Sheets, etc.), there is a possibility that, for example, inconveniences such as the inability to check the contents may occur.

[0004]

SUMMARY OF THE INVENTION The problem to be solved by the present invention is to solve the above-mentioned problems of the prior art, and to contain an economical amount of a bioactive substance, and not to impair the characteristics of the base polymer. An object of the present invention is to obtain a biodegradable resin composition having an active function and a molded product.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, when adding a bioactive substance to an aliphatic polyester, a specific compound was added together. As a result, it has been found that a resin composition having a function of exhibiting high biological activity can be obtained even when the amount of the bioactive substance added is small, and the present invention has been completed. The present invention provides the following [1] to [1]
4].

[1] A biodegradable resin composition containing a migration promoter, an aliphatic polyester, and a bioactive substance. [2] A biodegradable resin composition containing 5 to 50% by weight of a migration accelerator, 94.9999 to 40% by weight of an aliphatic polyester, and 0.000001 to 10% by weight of a bioactive substance. [3] The aliphatic polyester is an aliphatic hydroxycarboxylic acid, a cyclic ester of an aliphatic hydroxycarboxylic acid, an aliphatic polyhydric alcohol and an aliphatic polybasic acid, and two or more monomers selected from the group consisting of The biodegradable resin according to [1] or [2], which is obtained by polymerizing at least one selected from the group consisting of a body and / or an oligomer and / or a polymer obtained by polymerizing these monomers. Composition.

[4] The aliphatic hydroxycarboxylic acid is
Lactic acid, glycolic acid, and at least one selected from the group consisting of 6-hydroxycaproic acid,
The biodegradable resin composition according to [3]. [5] The biodegradable resin composition according to [3] or [4], wherein the aliphatic polybasic acid is at least one selected from the group consisting of succinic acid, adipic acid, fumaric acid, and maleic acid. [6] The aliphatic polyhydric alcohol is ethylene glycol, 1,4-butanediol, diethylene glycol,
The biodegradable resin composition according to any one of [3] to [5], which is triethylene glycol. [7] The biodegradable resin composition according to any one of [1] to [6], wherein the migration accelerator has an SP value of 18 to 23 (J / cm ³ ) ^1/2 .

[8] The method according to any one of [1] to [6], wherein the migration promoter is at least one selected from the group consisting of triacetin, tributyl acetylcitrate, triethylene glycol diacetate, and polyethylene glycol. 2. The biodegradable resin composition described in 1. above. [9] The bioactive substance according to any one of [1] to [8], wherein the bioactive substance is at least one selected from the group consisting of insecticides, antibacterial agents, bactericides, fungicides, and repellents. Biodegradable resin composition. [10] The biologically active substance is 18 to 23 (J / cm ³ )
^The biodegradable resin composition according to any one of [1] to [9], which has an SP value of ^1/2 .

[11] The biodegradable resin composition according to any one of [1] to [9], wherein the bioactive substance is etofenprox. [12] A molded product comprising the resin composition according to any one of [1] to [11]. [13] The molded article according to [12], wherein the molded product is at least one selected from the group consisting of a film, a fiber, a monofilament, a multifilament, a woven fabric, a nonwoven fabric, and a net. [14] The molded product according to [12], wherein the molded product is a composite composed of at least one selected from the group consisting of a film, a fiber, a monofilament, a multifilament, a woven fabric, a nonwoven fabric, and a net.

[0010]

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 of aliphatic hydroxycarboxylic acid (for example, polylactic acid, polyglycolic acid, polycaproic acid, poly (3-hydroxybutyric acid), etc.) and a copolymer (for example, lactic acid). , Glycolic acid copolymer, lactic acid and caproic acid copolymer, 3-hydroxybutyric acid and 3-hydroxyvaleric acid copolymer), homopolymer of aliphatic polyhydric alcohol and aliphatic polycarboxylic acid (for example, polybutylene succinate) , Polyethylene adipate, etc.) and copolymers (eg, butanediol and succinic acid and adipic acid copolymers, ethylene glycol and butanediol and succinic acid copolymers), aliphatic hydroxycarboxylic acids and aliphatic polyhydric alcohols and aliphatic polyhydric acids Consists of carboxylic acids Polymers (e.g., block copolymer of polylactic acid and polybutylene succinate), and mixtures thereof. 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. At least a part thereof may have any structure such as a linear, annular, branched, star, and three-dimensional network structure, and there is no limitation.

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

[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 undecandioic acid and dodecandioic acid, 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,
Examples include 1,9-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 shows substantially sufficient mechanical properties when it is formed into a target use, for example, a molded article such as a packaging material and a container. The molecular weight is not particularly limited as long as it is one. As the molecular weight of the aliphatic polyester, generally, as a weight average molecular weight,
It is preferably from 1 to 5,000,000, more preferably from 3 to 3,000,000, more preferably from 5 to 2,000,000, further preferably from 7 to 1,000,000, and most preferably from 9 to 500,000. In general,
If the weight average molecular weight is less than 10,000, the mechanical properties are not sufficient, or if the molecular weight is more 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 its production method,
Solvent type, catalyst type and amount, reaction temperature, reaction time,
It can be controlled to a desired one by appropriately selecting reaction conditions such as a method of treating the solvent distilled off by azeotropic distillation and 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 the method for producing an aliphatic polyester having lactic acid as a structural unit, see, for example, JP-A-7-173.
No. 266, and the methods described in Production Examples 3 to 6 described below. 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.

[Transfer Accelerator] The transfer accelerator used in the present invention is not particularly limited as long as it is a compound compatible with the aliphatic polyester. Specific examples of the transfer accelerator in the method of the present invention include, for example, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, dioctyl phthalate Decyl, diisodecyl phthalate, butylbenzyl phthalate,
Phthalates such as dicyclohexyl phthalate, di-i-butyl adipate, di-n-hexyl adipate, di-n-octyl adipate, di-adipate
2-ethylhexyl, di-n-butyl sebacate, di-2-ethylhexyl sebacate, di-2-azelate
Aliphatic dibasic acid esters such as ethylhexyl, phosphates such as diphenyl-2-ethylhexyl phosphate and diphenyloctyl phosphate, tributyl acetyl citrate, tri-2-ethylhexyl acetyl citrate, tributyl acetyl citrate , Methyl polyacetyl ricinoleate, butyl acetyl ricinoleate, hydroxy polycarboxylic acid esters such as butyl phthalyl butyl glycolate, butyl oleate, fatty acid esters such as amyl stearate, glycerin triacetate, glycerin tripropionate, Polyhydric alcohol esters such as glycerin monooleate, diethylene glycol dibenzoate, triethylene glycol di-2-ethyl butyrate, and triethylene glycol dicaprylate S, epoxidized soybean oil, epoxy compounds such as epoxy stearic octyl, polypropylene glycol adipate, poly ether esters such as polypropylene glycol sebacic acid ester. In addition, chlorinated paraffin, dinonylnaphthalene, toluenesulfonethylamide, camphor, methyl abietate and the like can be mentioned.

Other specific examples of the migration promoter in the method of the present invention include polyalkylene glycols such as polyethylene glycol and polypropylene glycol. The weight average molecular weight of the polyalkylene glycol is preferably from 0.1 to 1,000,000, more preferably from 0.2 to 500,000, even more preferably from 0.3 to 300,000.
0.4 to 100,000 is most preferable. In addition, the migration promoter used in the present invention has an SP value of 16 to 25 (J / J) from the compatibility with a resin or a biologically active substance and the migration promoting effect.
cm ³ ) ^1/2 , preferably 18 to 23 (J / cm ³ ) ^1/2 ,
More preferably, it is 19 to 22 (J / cm ³ ) ^1/2 .

[Amount of Addition of Migration Accelerator] The addition amount of the migration accelerator is generally 5% by weight or more, preferably 10 to 50% by weight, more preferably 15% by weight, based on the whole resin composition. ３０30% by weight. Usually, when it is less than 5% by weight, the effect as a migration promoter becomes insufficient. Normal,
Conversely, if it is too large, the appearance and physical properties may change.

[Bioactive substance] The bioactive substance used in the present invention includes insecticides, fungicides (bactericides, antibacterials,
Antifungal agents), herbicides, repellents and the like. Insecticides Specific examples of insecticides include, for example, organophosphorus insecticides such as MEP, diazinon, pyridafenthion, EPN, carbamate insecticides such as carbaryl, metolcarb, isoprocarb, fenobucarb, carbosulfan, cycloprothrin, Pyrethroid insecticides such as etofenprox and halofenprox; nereistoxin insecticides such as bensultap; chloronicotyl insecticides such as imidacloprid, nitenpium and acetamiprid; phenylpyrazole insecticides such as fipronil; and macrolides such as spinosad. Insecticides, pyrrole insecticides such as chlorfenapyr, insect growth regulators such as buprofezin, pyriproxyfen, cyromazine, acaricides such as propargite and phenothiocarb, and other paradicrols Examples thereof include benzene, naphthalene, camphor, octachlorodipropyl ether, and hinokitiol.

Disinfectants Specific examples of disinfectants include copper disinfectants such as copper oxine, organic sulfur disinfectants such as zineb and maneb, organic chlorine disinfectants such as captan and chlorothalonil, thiophanate methyl, benomyl and carbendazole. , Benzimidazole fungicides such as thiabendazole, dicarboximide fungicides such as iprodione, vinclozolin, procymidone, acid amide fungicides such as flametopyr, phenylpyrrole fungicides such as fludioxonil, and morpholine fungicides such as dimethomorph. Biosynthetic agents such as methoxyacrylate fungicides such as azoxystrobin, kresoxim-methyl, and oliverite; anilinopyrimidine fungicides such as mepanipyrim, cyprodinil, and pyrimethanil; triadimefon and triflumizole Harm agent, chloropicrin, soil fungicides such as PCNB, other fluazinam, o- phenylphenol (OP
P), diphenyl, chlorodiphenyl, cresol,
1,2-bis (bromoacetoxy) ethane, cinnamaldehyde, phenyl acetate, allyl isocyanate, α-methylacetophenone, thymol, perchlorocyclopentadiene, bromoacetic acid, 2,2-dibromo-3-nitrilepropionamide, chloro Examples include ethyl acetate, butyl chloroacetate, methyl chloroacetate, 5-chloro-2-methylisothiazolin-3-one, glutaraldehyde, and hinokitiol.

Herbicides Specific examples of herbicides include, for example, phenoxyacid herbicides such as naproanilide and fluazifop; carbamate herbicides such as chlorpropham and benthiocarb; acid amide herbicides such as propanil and napropamide; diuron;
Urea herbicides such as linuron, bensulfuron-methyl,
Sulfonylurea herbicides such as furazasulfuron, azimsulfuron, cyclosulfamuron and ethoxysulfuron; triazine herbicides such as simazine, atrazine, simethrin and hexazinone; diazine herbicides such as terbasil and bentazone; oxadiazon; Diazole herbicides, dinitroaniline herbicides such as trifluralin and prodiamine; aromatic carboxylic acid herbicides such as dicamba and imazapyr; fatty acid herbicides such as dalapon; organophosphorus herbicides such as piberphos and anilofos; Allyloxyphenoxypropionic acid herbicides such as cyhalofop butyl; thiocarbertic herbicides such as esprocarb; pyrimidyloxy herbicides such as pyriminobac-methyl; and others, ioxinil, capfentrol, epoprodan, and the like. It is.

[SP value of biologically active substance] The SP value of the biologically active substance used in the present invention is not particularly limited. The SP value of the bioactive substance used in the present invention is generally
From the viewpoint of the compatibility with the resin or the migration promoter and the effect of expressing the activity, 16 to 25 (J / cm ³ ) ^1/2 is preferable, and 18 to
23 (J / cm ³ ) ^1/2 is more preferable, and 19 to 22 (J
/ Cm ³ ) ^1/2 is more preferred. In addition, in consideration of the efficacy and residual toxicity of the biologically active substance, generally, as the insecticide, pyrethroid insecticides such as etofenprox and halofenprox are preferable, and particularly, etofenprox is preferable.

[Addition amount of bioactive substance] The addition amount of the bioactive substance varies depending on the type of the active substance, but is usually 0.01% by weight or more, preferably 0.1% by weight, based on the whole resin composition. 5 to 10% by weight, more preferably 1 to 5
% By weight. If the added amount is small, the obtained molded product does not exhibit a sufficient biological activity function. On the other hand, if the addition amount is too large, the biologically active substance is often expensive, so that the obtained molded product becomes expensive.

[Inorganic Additives] The molded article produced by the production method of the present invention has an improved crystallization rate, improved heat resistance,
In order to improve various physical properties such as 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, SiO ₂ , and clay, but it is necessary to appropriately select conditions (addition amount, particle size) so as not to impair the transparency of the molded article. There is. If transparency of the molded body is required, it is generally recommended to select a particle size substantially smaller than the wavelength of visible light. More specifically, for the purpose of improving the physical properties of blocking resistance, for example, SiO ₂ having a particle size of 1 to 50 nm is suitably used without impairing the transparency. In the production method of the present invention, when the aim 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 molded body, the SiO ₂ component 10
A crystalline inorganic substance containing at least about 10% by weight is preferable. Specifically, Talc TM-30 (manufactured by Fuji Talc), Kaolin J
P-100 (made by Tsuchiya Kaolin), NN kaolin clay (made by Tsuchiya Kaolin), Kaolinite ASP-170
(Manufactured by Fuji Talc), Kaolin UW (manufactured by Engelhard), Talc RF (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 not particularly limited, but when transparency is required, the amount is preferably 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less based on the resin composition. .

[Additives] In the molded article produced by the production method of the present invention, various elastomers (SBR, NBR, SBS type ternary block copolymer thermoplastic elastomer) may be used as long as the transparency of the molded article is not impaired. ), Additives (pigments, stabilizers, antistatic agents, ultraviolet absorbers, antioxidants, flame retardants, mold release agents, lubricants, dyes), fillers (impact core / shell particles, impact modifiers) Etc.) and pigments (metallic pigments, pearl pigments) can be used as appropriate according to the purpose and application.

[Molding / Processing Method] <Mixing / Kneading / Kneading> In the present invention, an aliphatic polyester composition is produced by mixing, kneading and kneading a biodegradable polymer, a bioactive substance and a migration promoter. The method may be a publicly known kneading technique, for example, a method in which each raw material is mixed in a solid state with a Henschel mixer, a ribbon blender, or the like, or a method in which the polymer is further kneaded using an extruder or the like while melting the polymer. it can.

<Molding> As a molding method for obtaining a molded article having a bioactive function of the present invention, generally, injection molding,
Extrusion molding, blow molding, inflation molding, profile extrusion molding, injection blow molding, vacuum pressure molding, spinning, and other ordinary methods can be mentioned, but the resin composition shown in the present invention can be applied to any molding method. There are no restrictions. The aliphatic polyester molded article having a bioactive function and degradability of the present invention includes injection molded articles, films, bags, tubes, sheets, cups, bottles, trays, yarns and the like obtained by known and publicly used molding methods. There are no restrictions on the shape, size, thickness, design, and the like. 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, a bottle for dairy products, soft drinks and alcoholic beverages, a wrap film, a cosmetic container, Garbage bags, caps, tents, tarpaulins, (adhesive) tapes, air mats, bleach containers, liquid detergent bottles,
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, containers and packaging for seeds and seedlings It can be used for materials and capsules, agricultural and horticultural films, product packaging films, overhead projector films, heat ray reflective films, liquid crystal display films, and the like. In addition, the film or sheet obtained by the method of the present invention is made into a laminate having a multilayer structure by laminating or bonding with a sheet of another material such as paper or another polymer by an adhesive or heat fusion. You can also.

[0030]

[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-10AD Detector: Shimadzu RID-6A Column: Hitachi Chemical GL-S350DT-5, GL-
S370DT-5 Solvent: chloroform Concentration: 1% Injection volume: 20 μl

[Production Example 1] <Production of Polymer A (poly L-lactic acid)> Dien-St
In a 100 liter reactor equipped with an ark trap,
10 kg of 90% L-lactic acid at 150 ° C./50 mmHg
After distilling off water while stirring for 6.2 hours, 6.2 g of tin powder was added, and the mixture was further stirred at 150 ° C./30 mmHg for 2 hours to oligomerize. To this oligomer were added 28.8 g of tin powder and 21.1 kg of diphenyl ether, and the mixture was added at 150 ° C./35.
A mmHg azeotropic dehydration reaction was performed, 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,
46 kg of molecular sieve 3 of the organic solvent to be returned to the reactor
The reaction was carried out at 150 ° C./35 mmHg for 40 hours by passing through the column filled with A and returning to the reactor to obtain a solution of polylactic acid having a weight average molecular weight of 146,000. To this solution was added 44 kg of dehydrated diphenyl ether, diluted and cooled to 40 ° C., and the precipitated crystals were filtered.
Wash three times with 10 kg of n-hexane, 60 ° C / 50m
Dried at mHg. This powder is mixed with 0.5N-HCl 12k
g and 12 kg of ethanol, stirred at 35 ° C. for 1 hour, filtered, and dried at 60 ° C./50 mmHg to obtain 6.1 kg (85% yield) of polylactic acid as a white powder. The weight average molecular weight Mw of this polylactic acid (polymer B) is 14.
It was 50,000.

[Production Example 2] <Production of polymer B (polybutylene succinate)>
In a 00 liter reactor, 1,4-butanediol 5.
05 kg, 6.65 kg of succinic acid, 293.0 kg of diphenyl ether, and 0.1 kg of tin oxide were added.
The mixture was heated and stirred while distilling water out of the system at 140 mmHg for 7 hours to form an oligomer. To this, Dean-Star
Attach k trap, 140 ° C / 30mmHg for 2
Azeotropic dehydration for 4 hours, and then return 4 parts of organic solvent to the reactor.
After passing through a column packed with 0 kg of molecular sieve 3A and returning to the reactor, 130 ° C./17 mmH
The reaction was carried out for 40 hours with g, to obtain a solution of polylactic acid having a weight average molecular weight of 123,000. To this solution was added 44 kg of dehydrated diphenyl ether, diluted and cooled to 40 ° C., and the precipitated crystals were filtered, washed three times with 10 kg of n-hexane, and dried at 60 ° C./50 mmHg. The powder was added with 12 kg of 0.5N HCl and 12 kg of ethanol, stirred at 35 ° C. for 1 hour, filtered, and dried at 60 ° C./50° C.
Drying at mmHg yielded 8.7 kg (90% yield) of white powdered polybutylene succinate. Weight average molecular weight Mw of this polybutylene succinate (Polymer B)
Was 118,000.

[Production Example 3] <Production of Polymer C (Polybutylene succinate / polylactic acid copolymer)> 120.0 g of polylactic acid of Production Example 1, 80.0 g of polybutylene succinate of Production Example 2, 800 g of diphenyl ether , 0.7 g of metallic tin, 13
The dehydration condensation reaction was performed at 0 ° 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 188 g of a copolymer of polybutylene succinate and polylactic acid.
(94% yield). The weight average molecular weight Mw of this copolymer of polybutylene succinate and polylactic acid (copolymer C) was 14,000.

[Production Example 4] <Copolymer D (Polycaproic acid / polylactic acid copolymer)>
Production> The reaction was carried out in the same manner as in Production Example 1 except that 6-hydroxycaproic acid was used instead of L-lactic acid, and as a result, polycaproic acid (weight average molecular weight Mw was 15.0)
10,000). Next, 20.0 g of the obtained polycaproic acid and 180.0 g of polylactic acid (the weight average molecular weight Mw was 14.5)
) To obtain a copolymer (copolymer F) of polycaproic acid and polylactic acid. The yield was 92% and the weight average molecular weight Mw was 153,000.

B. Evaluation method The condition method of the evaluation performed using the molded article of the resin composition manufactured using the aliphatic polyester obtained in Production Examples 1 to 4 is as follows. Insecticidal test A deep petri dish was placed on the test resin, and 10 adult German cockroaches (Blattella germanica) were placed in the deep petri dish and two days later, dead insects were examined.

Antifungal test Poterodextrose agar medium was poured into a sterilized petri dish to prepare an agar plate. The test resin was placed in the center of the agar plate, and the flora disk of the test paper fungus was inoculated near the resin. Untreated, the center of the agar plate was inoculated with a flora disk of the test filamentous fungus. After culturing at 24 ° C. for 7 days, the flora length was measured,
The antifungal activity of the test resin was determined. [Three test filamentous fungi] Cladosporium herbarum (CH) Aspergillus niger (AN) Penicillium citrinum (PC) Antibacterial test A bouillon agar medium was poured into a sterilized petri dish to prepare an agar plate. Place the test resin in the center of the agar plate,
The test bacteria were inoculated in the vicinity of the resin by the streaking method.
The antibacterial activity was determined by observing the growth inhibition status after culturing for one day. [4 types of test bacteria] Pseudomonas aeruginosa (PA) Proteus vulgaris (PV) Bacillus cereus (BC) Escheichia coli (EC) Weeding test 1/5000 Wagner pots were filled with field soil (sand loam) and seeded with the following weeds One day later, the polymer obtained in the production example was used as a raw material, and a coating treatment was performed with a resin film having a large number of holes each having a diameter of 5 mm and formed at intervals of 2 cm, and the herbicidal effect was examined 30 days later. [Weeds] Meishishiba (A) Shiroza (B) Purslane (C) Ichibai (D) Aobeyu (E) Twigweed (F) Salix (G) Rosewood (H) White clover (I) Examples and Comparative Examples In the following examples, when the molded body is subjected to heat treatment,
If the crystallization in the mold is performed at the time of cooling, the temperature should be set within the range from the crystallization start temperature at the time of cooling to the crystallization end temperature or more, and after the molding, the crystallization is performed at the time of the temperature increase by the heat treatment operation. If so, the temperature was set within the temperature range from the glass transition temperature to the melting point.

Examples 1 to 30 The polylactic acid or each copolymer obtained in Production Examples 1 to 4 were mixed with a bioactive substance and a migration promoter in a ratio shown in Table 1 [Tables 1 and 2] using a Henschel mixer. After that, the extruder cylinder set temperature 170
The pellet was formed under the condition of ~ 210 ° C. 1 pellet
Melted at 80 ° C for 2 min, and then 180 ° C / 100
to obtain a film having a pressed thickness 150μm in kgf / cm ² / 1min. The results of each test performed using this film are shown in Tables 3 to 6 [Tables 4 to 7].

Comparative Examples 1 to 10 Pellets were obtained in the same manner as in Examples 1 to 30, except that no migration accelerator was added. The results of each test performed using this film are shown in Tables 3 to 6 [Tables 4 to 7] similar to the examples.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

[0045]

[Table 6] −: No growth +: Growth equivalent to no treatment

[0046]

[Table 7] [Weed control rate] 0: 0 to 9% 6: 60 to 69% 1: 10 to 19% 7: 70 to 79% 2: 20 to 29% 8: 80 to 89% 3: 30 to 39% 9: 90 to 90 99% 4: 40-49% 10: 100% (complete death) 5: 50-59%

[0047]

The results of any of the tests show that the effect of the biologically active substance was not observed in the absence of the migration promoter, and that the effect increased as the amount of the migration promoter increased.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yutaka Kubota 1144 Togo, Mogo-shi, Chiba Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Atsushi Kishi 1144 Togo, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd. 72) Inventor Takeshi Imakita 1144 Togo, Mobara-shi, Chiba Mitsui Toatsu Chemicals Co., Ltd.

Claims (14)

[Claims] 1. A biodegradable resin composition containing a migration promoter, an aliphatic polyester, and a bioactive substance. 2. A biodegradable resin composition containing 5 to 50% by weight of a migration promoter, 94.9 to 40% by weight of an aliphatic polyester, and 0.01 to 10% by weight of a bioactive substance. 3. The aliphatic polyester according to claim 1, wherein the aliphatic polyester is at least two members selected from the group consisting of aliphatic hydroxycarboxylic acids, cyclic esters of aliphatic hydroxycarboxylic acids, aliphatic polyhydric alcohols and aliphatic polybasic acids. The biodegradable resin according to claim 1, wherein the biodegradable resin is obtained by polymerizing at least one selected from the group consisting of monomers and / or oligomers and / or polymers obtained by polymerizing these monomers. Composition. 4. The method of claim 1, wherein the aliphatic hydroxycarboxylic acid is lactic acid,
The biodegradable resin composition according to claim 3, which is at least one selected from the group consisting of glycolic acid and 6-hydroxycaproic acid. 5. The biodegradable resin composition according to claim 2, wherein the aliphatic polybasic acid is at least one selected from the group consisting of succinic acid, adipic acid, fumaric acid, and maleic acid. 6. The biodegradable resin composition according to claim 3, wherein the aliphatic polyhydric alcohol is ethylene glycol, 1,4-butanediol, diethylene glycol, or triethylene glycol. 7. The method according to claim 7, wherein the migration promoter is 18 to 23 (J / c).
m ³ ) having an SP value of ^1/2.
The biodegradable resin composition according to any one of the above. 8. The method according to claim 1, wherein the migration promoter is at least one selected from the group consisting of triacetin, tributyl acetylcitrate, triethylene glycol diacetate, and polyethylene glycol. Biodegradable resin composition. 9. The method according to claim 1, wherein the biologically active substance is at least one selected from the group consisting of an insecticide, an antibacterial agent, a bactericide, a fungicide, and a repellent. Biodegradable resin composition. 10. The method according to claim 10, wherein the biologically active substance is 18 to 23 (J / c).
m ³ ) having an SP value of ^1/2.
The biodegradable resin composition according to any one of the above. 11. The biodegradable resin composition according to claim 1, wherein the bioactive substance is etofenprox. 12. A molded product comprising the resin composition according to claim 1. 13. The molded article according to claim 12, wherein the molded product is composed of at least one selected from the group consisting of a film, a fiber, a monofilament, a multifilament, a woven fabric, a nonwoven fabric, and a net. 14. The molded product according to claim 12, wherein the molded product is a composite composed of at least one selected from the group consisting of a film, a fiber, a monofilament, a multifilament, a woven fabric, a nonwoven fabric, and a net. .