ALIPHATIC COPOLYMER, PRODUCTION PROCESS, ALIPHATIC POLYESTER RESIN COMPOSITION, VARIOUS USES, COATING COMPOSITION, AND AGRICULTURAL OR HORTICULTURAL PARTICULATE COMPOSITION COMPRISING DEGRADABLE COATING FILM

Abstract: In the present invention, there are obtained aliphatic polyesters having a controlled thermal decomposing property, hydrolizability, and biodegradability, in which OH terminals and COOH terminals are decreased to 50% and 30%, respectively, through a ring-opening polymerization of a lactone and lactide by a mono alcohol having a high boiling point or a metal alkoxide, or by further decreasing both terminals through combining produced polymer terminals with a diisocyanate and, from a composition containing the polyesters, there is obtained a particle-state composition for agriculture and gardening in which a duration period of a fertilizing effect can be controlled, and which is not remained in soil by decomposition. From a resin primarily containing fatty acid cellulose ester derivatives, there are obtained a base film for a marking film which does not include a problem such as volatilization and migration of a plasticizer and a picture image formable heat-sensitive transfer recording material which is excellent in strippability, coloring concentration, and brightness, a conductive coating composition which is excellent in storage stability, adhesion, and conductivity, a single-liquid type coating and a moisture-curable graft copolymer, and a coating composition which have a non toxicity and nonirritating property and which are excellent in dryability. A copolymer in which average chain length in lactone and lactide units are controlled is excellent in heat resistance and impact resistance.

Description: TECHNICAL FIELD No. I of the present invention relates to aliphatic polyesters having a controlled thermal decomposition property, hydrolyzability, and biodegradability, and a method for the preparation thereof. In more detail, it relates to aliphatic polyesters which comprise polymerizing a cyclic ester monomer using a monoalcohol as an initiator, aliphatic polyesters in which terminal groups are modified, and a method for the preparation thereof. Further, No. II of the present invention relates to a particle-state fertilizer coated by a degradable thin layer which comprises a biodegradable terminal-controlled aliphatic polyester which comprises a monomer unit of at least any one of a lactone and lactide, in which proportion of the number of an alcohol-terminal is not more than 50% and/or proportion of the number of a carboxylic acid-terminal is not more than 30%. TECHNICAL BACKGROUND (the No. I of the present invention) In recent years, treatment of waste plastics is becoming a social problem, and recycling of plastics material and biodegradable plastics are paid attention. An aliphatic polyester resin is one of materials which are largely desired owing to biodegradability. As one of the aliphatic polyester resins which are industrially produced, a polycaprolactone is known. A polycaprolactone having a low molecular weight is an important material as a raw material for a polyurethane, a paint, and a coating agent. A polycaprolactone having a high molecular weight is employed as a molded article such as a compost bag, fishing lines, tees for golf, and a hot-melt adhesive, etc. owing to biodegradability. Further, the aliphatic polyester has been widely employed as a preferred material also in uses such as a use for molding various portions of human body and a use by fitting to human body. For example, a gyps for medical care (JP-A-58081042 Official Gazette) and a face mask for irradiating radiation rays (JP-A-60215018 Official Gazette) have been known. It is known that although such the aliphatic polyester has a peculiar thermally-decomposing property, hydrolyzability, and biodegradability, etc., respectively, in the case of the uses, thermally-decomposing property, hydrolyzability, and biodegradability, decomposition or degradation rate become important depending upon the uses thereof, accordingly, their properties can be modified by various copolymerization. For example, the thermally-decomposing property, hydrolyzability, and biodegradability of the aliphatic polyesters are controlled by a copolymerization of a lactone with a lactide, a copolymerization of a lactone with a glycolide, a copolymerization of a lactone with a carbonate, a copolymerization of a lactone with a cyclic ester, a copolymerization of a lactone with a lactam and, or modification of composition ratio, etc. Still further, in a polycondensation type polyester, it is tried to highly-polymerize by an isocyanate compound (JP-A-04189823 and JP-A-05178955 Official Gazettes). However, since a polymer having a sufficiently high molecular weight can be obtained without a crosslinking reaction in the aliphatic polyester which is obtained by the ring-opening polymerization such as in the present invention, there was not investigated a reaction with an isocyanate compound, etc. In the case of controlling the thermally-decomposing property, hydrolyzability, and biodegradability of the aliphatic polyesters, although there can be obtained a polymer having a desired thermally-decomposing property, hydrolyzability, and biodegradability by copolymerization, there is a problem that the copolymerization also affects to various other physical properties, resulting in that there cannot be obtained a target polymer. (the No. II of the present invention) Hitherto, for the purpose of manifestation of a fertilizing effect depending upon growth of farm products, there have been developed various fertilizing effect-controllable fertilizers. Particularly, there have been disclosed and commercially-supplied a particle-state fertilizer in which a coating material is coated on the surface. As described in JP-B-95000505 Official Gazette, there have been proposed various fertilizing effect-controllable fertilizers in, for example, USP 3,295,950, JP-B-65028927, JP-B-69028457, GB Patent 815829, JP-B-62015832 and JP-B-67013681 Official Gazettes. However, it is taught that it is difficult to adjust an elution rate of fertilizing components in all the fertilizing effect-controllable fertilizers. On the other hand, JP-B-85021952 and JP-B-85003040 Official Gazettes disclose a method for forming a thin layer in which there is employed a coating material primarily containing a polyolefin, and in the case of coating the surface of particle-state fertilizers, a hot air is blown to dry together with spraying a solution of the coating material over the particle-state fertilizers. It is taught that the method is characterized in that an elution rate of the fertilizers can be controlled, and the above-described method is widely put into practice, in which a thin layer is formed over the surface of the particle-state fertilizers. Further, JP-B-85003040 and JP-A-55901672 Official Gazettes, etc. show that a function for controlling elution is maintained by dispersing inorganic powders such as talc and sulphur into a thin layer of the polyolefin-based resin and, at the same time, there is accelerated the degradation or decomposition of residual thin layer after elution. In the particle-state fertilizers which have been conventionally proposed, the coating layers do not cause degradation or decomposition, and even though those caused the degradation, those remain in soil, resulting in that it is anxious that those produce pollution in the growth of farm products, soil circumstances, and water for irrigation and river around fields. From that reason, there has been intensively desired a particle-state fertilizer in which a thin layer has degradability and a duration period of a fertilizing effect can be controlled. In such the degradable thin layer, degradability means degradation by light, oxygen, and microorganisms, etc. Particularly, in the conventional particle-state fertilizer coated, it is difficult to control the elution rate of fertilizing components, and there has been a drawback that the fertilizing period is apt to be readily affected by circumstances such as weather and soil. Further, it is pointed that the thin layer after elution of the fertilizing components remain in soil over a long time of period without degradation. For that reason, utilization of biodegradable resins has been often tried and, for example, JP-A-07033576 Official Gazette states a combination of a polycaprolactone, a polylactic acid, or an aliphatic polyester compound with cellulose derivatives, low molecular weight polyethylenes, and paraffins, etc. However, since the polycaprolactone to be employed in the case has a melting point of 60°C, blocking is occasionally caused in transport or storage of products. Further, the above-described JP-B-95000505 also likewise discloses particle-state fertilizers coated by a polycaprolactone. However, in the coating material such as the polycaprolactone and polylactic acid, since degradation of the coating materials is too quick, those are not preferred in the case of employing as a gradually-dischargeable fertilizer. The document JP 10 007484 A relates to a gradually-effectuating fertilizer using a polymer, it does not disclose a two-stage reaction as defined in the claims. EP-A-0 934 918 (equivalent of JP 11 116 371 A) does not relate to polyesters prepared from monohydric alcohols and a lactone or a lactide : neither does said document mention polymers which are "end-capped" with moieties having urethane, ether or amide bonds. WO 98 35631 A and BE-A-1001 149 do not teach a polymer having alcohol terminals of not more than 50 % and/or carboxylic terminals of not more than 30 %, whilst having "urethane bonds, ether bonds or amide bonds", as end-caps. Furthermore, none of the documents 'Macromolecular Engineering of polylactones and polylactides', Macromolecules, 1991, 24(5), 977-981, US Patent US-A-3 274 142, and European Patent Application EP-A-0 778 304, either mention or suggest polymers that are "end-capped" with moieties having urethane, ether or amide bonds as defined in the claims. The document FR 2,118,009 discloses polylactones which have blocked final groups, prepared by allowing a polylactone or a mixture of polylactones, or even a mixture of a polylactone and a lactone moromer, in the presence of a catalyst, with one or more modifiers which contain at least one ester group which is not incorporated in a lactone ring and which does not bear any reactive hydrogen substituents. According to the document, polylactones having ester end groups are prepared. However, the document does not disclose at all end-capping reaction by the use of a modifier consisting of an isocyanate compound, a carbodiimide compound, an isocyanurate compound, a Schiff base, and a cyclic ether as defined in the claims. The document US 4,071,507 does not also disclose at all end-capping reaction by the use of a modifier consisting of an isocyanate compound, a carbodiimide compound, an isocyanurate compound, a Schiff base, and a cyclic ether as defined in the claims. The document discloses a reaction product of a higher fatty acid or a polyfunctional alcohol with a lactone, a lactide, a glycolide, or a mixture thereof, however, no mention is made of the end-blocking of hydroxyl group or carboxylic group by an isocyanate compound or a cyclic ether such as an epoxy compound, etc., as defined in the claims. Furthermore, in JP 07 053683 A (equivalent to US 5,618,911 A), mere copolymers of a polyester having a high melting point with a polyester having a low melting point are still not sufficient from a viewpoint of practical uses. Finally, the article in Macromolecules, 1988, 21(2) 286-293, discloses that a lactone monomer is subjected to a ring-opening polymerization using various metal alkoxides, and a product contains alkyl ester end-groups, however, the document not disclose at all end-capping by the use of a modifier as defined in the claims. PROBLEM TO BE SOLVED BY THE INVENTION A purpose of the No. I of the present invention is to obtain an aliphatic polyester having a controlled thermal decomposition, hydrolizability, and biodegradability. Further, it is to modify a terminal of the aliphatic polyester without adversely affecting to other physical properties. A purpose of the No. II of the present invention is to obtain a particle-state composition for agriculture and gardening in which in the case of coating it on a fertilizer, etc., biodegradability rate in a thin layer can be appropriately controlled depending upon purposes thereof, a fertilizing duration period can be controlled and, after elution of fertilizing components, the thin layer is disintegrated and decomposed by microorganisms in soil without remaining in the soil, and, after a lapse of a cultivating period of farm products, the thin layer disappears. DISCLOSURE OF THE INVENTION As a result of an investigation in relation to a structure of terminal groups which is the purpose of the No. I in the present invention, the present inventors found out that an alcohol terminal (it means the presence of a hydroxyl group at terminal) or a carboxylic acid terminal (it means the presence of a carboxylic group at terminal) affects to a thermal decomposition property, hydrolizability, and biodegradability in a polymer chain obtained by a ring-opening polymerization of a cyclic ester monomer, that the above-described various properties can be controlled by decreasing the terminals, and that there can be obtained a preferred aliphatic polyester by modifying the terminals, particularly, by changing the polymer terminals to an alkyl group using an isocyanate, etc. after a ring-opening polymerization, and the present invention has been completed. That is, No. 1 of the present invention provides an aliphatic polyester, which is an aliphatic polyester composed of at least one kind of a monomer unit of any one of a lactone or a lactide, in which a proportion of the number of the alcohol terminals is not more than 50% based on the number of total terminals in the aliphatic polyester and/or a proportion of the number of the carboxylic acid terminals is not more than 30% based on the number of total terminals in the aliphatic polyester. No. 2 of the present invention provides an aliphatic polyester described in the No. 1 of the present invention in which a proportion of the number of the alkyl group terminals and/or alkenyl group terminals (herein, the alkyl group and/or alkenyl group are a group having a straight chain and cyclic or branched chain which contain a carbon number of 1-24 pieces) is not less than 30% based on the total terminals in the aliphatic polyester. No. 3 of the present invention provides an aliphatic polyester described in any one of the No. 1 or 2 of the present invention in which there is contained a bond produced by allowing to react a modifying agent with the alcohol terminals and/or carboxylic acid terminals in 0.2-40 pieces on average based on one molecule of a polymer after modifying. No. 4 of the present invention provides an aliphatic polyester described in No. 4 of the present invention in which the bond produced by allowing to react the modifying agent is at least one selected from the group consisting of urethane bond, ether bond, ester bond, and amide bond. No. 5 of the present invention provides a method for the preparation of an aliphatic polyester by adjusting a proportion of the number of the alcohol terminals to not more than 50% and/or a proportion of the number of the carboxylic acid terminals to not more than 30% based on the number of total terminals, in which at least one kind of a lacton or lactide is polymerized by ring-opening using at least one kind of a monoalcohol having a high boiling point or a metal alkoxide as an initiator. No. 6 of the present invention provides a method for the preparation of an aliphatic polyester described in the No. 5 of the present invention in which a bond produced by allowing to react a modifier to terminals in the aliphatic polyester having the alcohol terminals and/or the carboxylic acid terminals is contained in 0.2-40 pieces on average. In relation to the purpose of the No. II of the present invention, as a result of an intensive investigation concerning a selection of a material for a thin layer in order to prepare a particle-state fertilizer coated by a degradable thin layer having degradability in which duration period of a fertilizing effect can be widely controlled, the present inventors found out that a terminal-controlled aliphatic polyester is appropriate as a coating layer for a gradually-dischargeable fertilizer, and the present invention has been completed. That is, No. 7 of the present invention provides a particle-state composition for agriculture and gardening characterized in that surface of a particle-state fertilizer is coated by a coating material II-A alone or a mixture of the coating material II-A with a coating material II-B, the coating material II-A is composed of a terminal-controlled aliphatic polyester, the terminal-controlled aliphatic polyester is an aliphatic polyester composed of at least one kind of monomer units of any one of a lactone or a lactide, and in which a proportion of the number of the alcohol terminals is not more than 50% based on the number of total terminals in the aliphatic polyester and/or a proportion of the number of the carboxylic acid terminals is not more than 30% based on the number of total terminals in the aliphatic polyester, the coating material II-B is composed of at least one kind of selected from the group consisting of an olefine polymer, a copolymer containing an olefine, a vinylidene chloride polymer, a copolymer containing vinylidene chloride, a diene-based polymer, waxes, a petroleum resin, a natural resin, a cellulose acetate resin, a polycaprolactone, oils & fats and a modified product therefrom. No. 8 of the present invention provides a particle-state composition for agriculture and gardening described in the No. 7 of the present invention, in which a proportion of the number of the alkyl group terminals and/or alkenyl group terminals (herein, the alkyl group and/or alkenyl group is a group having a straight chain and cyclic or branched chain which contain a carbon number of 1-24 pieces) is not less than 30% based on the total terminals in the aliphatic polyester. No. 9 of the present invention provides a particle-state composition for agriculture and gardening described in any one of the No. 7 or 8 of the present invention, in which the terminal-controlled aliphatic polyester is an aliphatic polyester obtained by allowing to react a modifier with the alcohol terminals and/or the carboxylic acid terminals in an aliphatic polyester composed of at least one kind of monomer units of a lactone or a lactide, and bonds produced by allowing to react the modifier are contained in 0.2-40 pieces on average based on one molecule of a polymer after modifying. No. 10 of the present invention provides a particle-state composition for agriculture and gardening described in the No. 9 of the present invention, in which the bonds produced by allowing to react the modifier is at least one kind selected from the group consisting of a urethane bond, an ether bond, an ester bond, and an amide bond. No. 11 of the present invention provides a particle-state composition for agriculture and gardening described in the No. 7 of the present invention, in which the coating material II-B is a polycaprolactone, a cellulose acetate, or a mixture thereof. No. 12 of the present invention provides a particle-state composition for agriculture and gardening described in the No. 7 or 11 of the present invention, in which there are further added inorganic fillers and/or additives for resins. No. 13 of the present invention provides a particle-state composition for agriculture and gardening described in the No. 12 of the present invention, in which the inorganic fillers are talc, calcium carbonate, or a mixture thereof. BRIEF DESCRIPTION OF DRAWINGS Figures 1-6 represent a graph showing results of Table 1-1 in the No. I of the present invention. Figure 7 is an outlined drawing showing one example of an apparatus which is appropriate for the preparation of an article of the No. II of the present invention. Brief explanation of marks in the Figure 7 1 Spraying tower 2 Throwing inlet for a fertilizer 3 Outlet for blowing waste gas 4 Nozzle for a fluid 5 Pump 6 Valve 7 Outlet for discharging 8 Heat exchanger 9 Orifice flow meter 10 Blower 11 Liquid tank T 1 , T 2 , T 3 Thermometer SL Steam BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be illustrated in detail. First of all, the No. I of the invention is illustrated. As the cyclic ester monomer to be employed in the present invention, a lactone and lactide, etc. are enumerated. The lactone is a compound having an intramolecular cyclic ester structure and, specifically, there can be exemplified lactones such as β-propiolactone, β-butyrolactone, γ-butyrolactone, ε-caprolactone, γ-varelolactone, δ-varelolactone, α,α-dimethyl-β-propiolactone, β-ethyl-δ-varelolactone, α-methyl lactone, β-methyl-ε-caprolactone, γ-methyl-ε-caprolactone, 3,3,5-trimethyl- ε-caprolactone, 3,5,5-trimethyl-ε-caprolactone, enantolactone, and dodecalactone. Further, the lactide to be described in the present invention is a bimolecular cyclic ester of an aliphatic hydroxycarboxylic acid and, specifically, there can be exemplified glycolide, lactide, diethyl glycolide, dimethyl glycolide, α,α-dimethyl glycolide, L-lactide, D-lactide, D,L-lactide and MESO-lactide, etc. which are the bimolecular cyclic ester of lactic acid, glycol acid, ethyl glycol acid, dimethyl glycol acid, etc. In the present invention, the above-described cyclic ester monomers can be employed solely or in combination of two or more kinds. In the present invention, in the case of ring-opening polymerization of the above-described cyclic ester monomers, there are preferably employed the cyclic ester monomers having water content of not more than 80 ppm and an acid value of not more than 0.12 mg(KOH)/g. In the case of a monomer having the water content and the acid value exceeding the above values, it is difficult to adjust a carboxylic terminal of a polymer to not more than 30% because of an action as an initiator for ring-opening by water and an acid (hydroxyl acid). Further, it becomes difficult to allow to completely react even in capping of carboxylic acid or alcohol terminals, and it is incapable of attaining the purpose of the present invention. In the present invention, in the case of ring-opening polymerization of the above-described cyclic ester monomers, a monoalcohol and/or a metal alkoxide are employed as a polymerization initiator. When the lactone and lactide are ring-opening-polymerized by employing the monoalcohol as a polymerization initiator, an initiating terminal becomes a monoalkyl group, and a polymerized terminal becomes hydroxyl group. In the present invention, an alkyl terminal represents an alkyl group from the above-described monoalcohol. For example, when ∈-caprolactone is polymerized using ROH (R represents an alkyl group) as an initiator, there is obtained a polymer having a formula described below. RO(CO(CH 2 ) 5 O) n H Accordingly, although proportion of the number of the alcohol terminal becomes 50% with respect to the number of total terminals, when water is eliminated from the alcohol terminal, the proportion of the number of the alcohol terminal becomes not more than 50%. On the other hand, when the lactone and lactide are ring-opening-polymerized using the metal alkoxide as a polymerization initiator, an initiating terminal becomes a monoalkyl group, and a terminal of a polymer becomes a metal, and it becomes hydroxyl group by subjecting to hydrolysis. In the present invention, an alkyl terminal represents an alkyl group from the above-described metal alkoxide. For example, when ε-caprolactone is polymerized using M(OR) m (M represents a metal, and R represents an alkyl group) as an initiator, there is obtained a polymer having a formula described below. (RO(CO(CH 2 ) 5 O) n ) m M Metal terminal becomes an alcohol terminal by a post treatment such as neutralization and hydrolysis after polymerization. The monoalcohol to be employed is mono-ols having a carbon number of 1-24, preferably, mono-ols having a high boiling point of not less than 150°C. For example, there can be employed hexane, heptane, octane, butoxyethanol, phenol, ethoxyphenol, cyclohexanol, an alcohol having an alkenyl group such as hydroxyethyl acrylate, a reaction product of an alcohol with a lactone, a reaction product of an alcohol with a cyclic ether (for example, ethylene oxide and propylene oxide, butylene oxide, and styrene oxide, etc.), or a compound having one hydroxyl group at most. It is to be noted that the compound having one hydroxyl group at most is a product obtained by a ring opening polymerization of a lactone or lactide using a metal alkoxide which is an initiator and, a terminal of a polymer is a metal, and it becomes a hydroxyl group by hydrolysis, in which hydrolysis degree is low, and hydroxyl group is not more than 1. The initiators may be employed solely or even in combination of two or more kinds. In the case that the initiators are employed, a catalyst becomes required. As the catalyst, there are enumerated metal compounds such as Al, Ti, Sn, and Znwhich are usually employed, and it is not limited to the compounds. The compounds may be employed solely or even in combination of two or more kinds. As the metal alkoxide to be employed as an initiator in the present invention, specifically, there are enumerated aluminum alkoxide, titanium alkoxide, zinc alkoxide, tin alkoxide, zirconium alkoxide, yttrium alkoxide, samarium alkoxide, niobium alkoxide, neodymium alkoxide, and antimony alkoxide, etc. As the alkoxide, there are enumerated aliphatic or aromatic alkoxides having a carbon number of 1-24 such as a methoxide, an ethoxide, a propoxide, a butoxide, a phenoxide, and 2, 6-diisopropyl phenoxide. The alkoxides may be employed solely or even in combination of two or more kinds. As a compound for giving urethane bond, ether bond, ester bond, and amide bond to the aliphatic polyester of the present invention, there are enumerated an isocyanate compound such as a monoisocyanate, a diisocyanate, and a triisocyanate, a carbodiimide compound, an isocyanurate compound, a Schiff base, an anhydride such as succinic anhydride, a cyclic ether such as ethylene oxide, propylene oxide, butylene oxide, and an epoxide such as styrene oxide. At least one kind of the compounds are preferably and, for example, the cyclic ether and the isocyanate are preferably employed together. More preferably, the epoxide is desirably added after the completion of a reaction by adding the isocyanate. For example, by adding 1/2 molar ratio of the diisocyanate to a monofunctional alcohol-terminated aliphatic polyester obtained using a monoalcohol which is an initiator, an aliphatic polyester having alkyl groups at terminals is obtained by connecting through a urethane bond derived from 2 mols of the aliphatic polyesters. Further, by adding an epoxy compound such as butylene oxide, an alcohol terminal is produced together with formation of an ester bond in a carboxylic acid terminal, and an alcohol terminal is produced together with formation of an ether bond in an alcohol terminal. Accordingly, by a reaction of the alcohol terminals with an isocyanate, there is obtained an aliphatic polyester having an alkyl terminal at both terminals as well as the above description. In the case, there becomes smaller a proportion occupied by the alcohol terminal and the carboxylic acid terminal with respect to total terminals in the aliphatic polyesters, and there becomes larger an effect for a thermal degradability, hydrolizability, and biodegradability. Further, the urethane bond, ether bond, ester bond, or amide bond may be even remained at terminals of a polymer molecule, and a monoepoxy compound and monoisocyanate compound, etc. are employed for capping the terminals of a polymer chain produced and, a polyfunctional compound such as a diepoxy compound and diisocyanate compound is employed for coupling a polymer chain produced. The present invention also includes a polymer obtained by allowing to react a diisocyanate with both terminals of a diol-initiated aliphatic polyester and allowing to connect a mono-ol-initiated aliphatic polyester to residual isocyanate groups. In the present invention, an aliphatic polyester which is excellent in thermal disintegrabability, hydrolizability, and biodegradability can be obtained by the above-mentioned synthesis methods, and the present invention is not limited to those. Proportion of the alcohol terminals and carboxylic acid terminals is not more than 50% and not more than 30%, preferably not more than 20% and not more than 8%, and more preferably 0% and 0%, respectively, with respect to total terminals of the aliphatic polyester, by which there can be controlled thermal disintegrabability, hydrolizability, and biodegradability. In the case that it has the alcohol terminals and carboxylic acid terminals exceeding the above-described range (50%), thermal degradability, hydrolizability, and biodegradability become an identical extent to those obtained by a prior art, resulting in that the purpose of the present invention cannot be attained. In the present invention, it is desired to possess an alkyl group terminal and/or an alkenyl group terminal of not less than 30% with respect to total terminals, which have a straight chain, a ring, and a branch containing 1-24 carbons. In the case that the carbon number in the alkyl group and/or the alkenyl group exceeds 24, it affects to various physical properties of the aliphatic polyester, resulting in that the purpose of the present invention cannot be attained. Further, in the case that the alkyl group terminal and/or the alkenyl group terminal are not more than 30%, it becomes difficult to control the thermal degradability, hydrolizability, and biodegradability. It is to be noted that the alkyl group terminal in the present invention is derived from a monoalcohol which is an initiator, and derived from a modifier to be employed for capping the hydroxyl terminals and carboxylic acid terminals. Further, the alkenyl group terminal is derived from alcohol terminals by elimination of water, or derived from hydroxyethyl(meth)acrylate employed as an initiator and a modifier. In the present invention, the aliphatic polyester may even have 0.2-40 pieces of bonds other than ester bonds in one polymer molecule. That is, one polymer molecule after modifying has 0.2-40 pieces (on average) of bonds produced by modifying the alcohol terminals and/or carboxylic acid terminals through allowing to react a modifier with the aliphatic polyester. For example, if an alcohol-terminated polycaprolactone produced by polymerization of caprolactone using octanol which is an initiator is allowed to react with 1/2 equivalent of a diisocyanate, since two molecules of the polycaprolactone connect to each other through two urethane bonds, one molecular chain of a polymer after modifying results in containing two urethane bonds. The bonds are produced by controlling the terminals of a polymer chain, and the polymer is preferably controlled in a polymerization degree of 0.2-2% {(number of bond produced by modifying)/(polymerization degree of a lactone or lactide monomer)x100}. The bonds other than ester bonds, that is, in the case that the bonds produced by bonding to the modifier are too large amount than the above-described range, it affects to various physical properties of the aliphatic polyester, resulting in that the purpose of the present invention cannot be attained. In the present invention, solvents can be employed in the case of the ring-opening polymerization of the cyclic ester monomer. The solvents to be employed herein are not particularly limited if those are a compound which does not react with catalysts, initiators, and monomers. As the preferred solvents, there are enumerated an aromatic hydrocarbon such as toluene and xylene, and an aliphatic hydrocarbon such as hexane and cyclohexane. Further, in the present invention, the aliphatic polyester can be also prepared without using solvents in the case of the ring-opening polymerization of the cyclic ester monomer. In the present invention, the cyclic ester monomer can be polymerized by ring-opening through continuously supplying the cyclic ester monomer into a continuous polymerization apparatus. As the continuous polymerization apparatus to be employed, there can be employed a vessel type reactor equipped with an agitator, a plug-flow type reactor, and a combination thereof. More specifically, in addition to the vessel type reactor equipped with an agitator, there can be employed a static mixer type reactor, a column type reactor, and an extruder type reactor, etc. Further, the reactors can be employed in combination of two or more kinds. Hereinafter, the No. II of the present invention will be illustrated. The particle-state composition for agriculture and gardening of the present invention is a particle-state fertilizer characterized by being obtained spraying a solution composed of the above-described coating materials on the particle-state fertilizer and, by coating while simultaneously drying through blowing a high speed hot air stream to momentarily dry, and in which a coating layer has degradability and disintegrability, and a duration period of a fertilizing effect can be controlled. In the beginning, a terminal-controlled aliphatic polyester is illustrated which is employed as a coating material II-A in the present invention. As the terminal-controlled aliphatic polyester in the present invention, there is employed the aliphatic polyester of the No. I of the present invention. Materials employed as a coating material II-B in the present invention include at least one or more kinds of substances selected from the group consisting of an olefine polymer, a copolymer containing an olef ine, a vinylidene chloride polymer, a copolymer containing vinylidene chloride, a diene-based polymer, waxes, a petroleum resin, a natural resin, a cellulose acetate resin, a polycaprolactone, oils & fats and a modified product thereof. The olefine polymer includes a polyethylene, a polypropylene, an ethylene-propylene copolymer, a polybutene, a butene-ethylene copolymer, a butene-propylene copolymer, and a polystyrene, etc., the copolymer containing an olefine include an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, an ethylene-acrylate copolymer, an ethylene-methacrylate copolymer, an ethylene-carbon monoxide copolymer, and an ethylene-vinyl acetate-carbon monoxide copolymer, etc. The copolymer containing vinylidene chloride includes a vinylidene chloride-vinyl chloride based copolymer, and the diene-based polymer includes a butadiene polymer, an isoprene polymer, a chloroprene polymer, a butadienestyrene copolymer, an EPDM polymer, and a styrene-isoprene copolymer, etc. The waxes include bee waxes, wood waxes, and paraffins, etc., and the natural resin includes a natural rubber and rosins, etc. The cellulose acetate resin includes diacetates having an average substituent degree of 2.5 and triacetates having an average substitution degree of 2.9. The polycaprolactone is a polyester prepared by a ring-opening addition polymerization of ∈-caprolactone, and which has a molecular weight of not less than 10, 000, and preferably 50,000-100,000. The oils & fats and the modified product thereof are a hydrogenated oil, a solid fatty acid, and metal salts thereof, etc. Weight percentage of the coating material with respect to a coated particle-state substance (for example, a particle-state fertilizer) in the present invention, that is, coating ratio ranges preferably in 2-20% (by mass). Further, the coating material II-A is employed in a range of 10-100% (by mass) based on total of the coating material II-A and the coating material II-B, and preferably in a range of 50-100% (by mass), and the coating material II-B is employed in a range of 0-90% (by mass), and preferably in a range of 0-50% (by mass). It is to be noted that the coating material in the present invention can be optionally mixed with third coating layer components which are capable of being mixed. As such the third coating layer components (it is shown as coating material II-C in Table II-1 of Examples), there are enumerated additives for resins such as plasticizers, surface active agents as an elution controller, talc as insoluble fillers, calcium carbonate, and fillers such as metal oxides, etc. Mixture is required to be uniformly mixed. In the case of not being uniform, micro particles are partially one-sided and a continuous phase is lost in the coating materials, resulting in that an effect by the coating material is lost. Addition amount of the fillers which include talc, calcium carbonate, metal oxides, and a mixture thereof is 0-200 parts by weight, preferably 10-150 parts by weight, and more preferably 20-100 parts by weight based on 100 parts by weight of the coating material II-A alone or 100 parts by weight of the mixture of the coating material II-A with the coating material II-B. In the case of larger than the range, holes are apt to be formed in a coating thin layer, and an elution of the fertilizer cannot become controlled. In the present invention, a fourth component is further optionally employed for the coating thin layer. As the fourth component, for example, there can be enumerated a photo-degradation accelerator, a biodegradation accelerator, an elution controller, and cellulose powder, etc., and the components can be employed by uniformly dispersing. As the photo-degradation accelerator, for example, there can be exemplified benzoins, benzoin alkyl ethers, benzophenone and derivatives thereof such as benzophenone, and 4,4'-bis(dimethylamino)benzophenone; acetophenone and derivatives thereof such as acetophenone and α,α-diethoxyacetophenone; quinones; thioxanthone; a photo-exciting agent such as phthalocyanine, an anatase-type titanium oxide, an ethylene-carbon monoxide copolymer, and an accelerator such as an aromatic ketone and a metal salt thereof, etc. The photo-degradation accelerators can be employed solely or in combination of two or more kinds. By the use of the photo-degradation accelerators, a cellulose ester can be photo-decomposed. For that reason, biodegradability can be interdependently elevated upon the photo-degradability. As the accelerators for biodegradation, there are exemplified, for example, an organic acid such as an oxo acid (for example, an oxo acid having a carbon number of 2-6 or so such as glycolic acid, lactic acid, citric acid, tartaric acid, and malic acid), a saturated dicarboxylic acid (for example, a lower saturated dicarboxylic acid having a carbon number of 2-6 or so such as oxalic acid, malonic acid, succinic acid, succinic anhydride, and glutaric acid); a lower alkyl ester of the organic acids with an alcohol having a carbon number of 1-4 or so. A preferred accelerator for biodegradation includes citric acid, tartaric acid, and malic acid which are an organic acid having a carbon number of 2-6 or so. The accelerators for biodegradation are employed solely or in combination. Further, as the accelerators for biodegradation, there are also included a hydrolysis enzyme such as biodegradable enzyme, for example, lipase, cellulase, and esterase, etc. The biodegradable enzyme can be employed by suspending or dispersing in a solvent. It is to be noted that the above-mentioned accelerators for photodegradation can be employed together with the accelerators for biodegradation. Further, cellulose powder can be also mixed in order to prevent an aggregation of coated particles. In the present invention, the coating material is dissolved or dispersed in a solvent, and it is sprayed on the surface of the particle-state fertilizers while maintaining at a high temperature, and a high speed heated air stream is simultaneously blown to instantly dry and coat, whereby, the particle-state fertilizer can be obtained. As the solvents, there can be enumerated ketones such as acetone and 2-butanone (MEK), ketones such as cyclohexanone, esters such as methyl formate, methyl acetate, and ethyl acetate, and cyclic ethers such as THF and dioxane which are low in price and have an appropriate boiling point (70-90°C), and THF is more preferred from a viewpoint of an excellent solubility to the coating material II-A and the coating material II-B. Examples Hereinafter, although the present invention is specifically illustrated by Examples, the present invention is not limited to those. It is to be noted that "part" and "%" are shown by "part by mass" and "% by mass" except a case being specifically shown. Hereinafter, Examples are illustrated in relation to an aliphatic polyester of the No. I in the present invention and a method for the preparation thereof. A proportion occupied by an alcohol terminal and carboxylic acid terminal is merely shown by "%" based on total terminals of a polymer obtained. Thermal decomposition was evaluated by a molecular weight retention ratio at the temperature of 180 and 200°C and in a nitrogen atmosphere and air. Hydrolizability was evaluated by a molecular weight retention ratio of pellets after storing for a fixed period under a circumstance at the temperature of 40°C and humidity of 40% and a circumstance at the temperature of 60°C and humidity of 80%. Evaluation of biodegradability was conducted using powder of a polymer obtained by a method using an active sludge according to JIS K6950. Tensile test was conducted according to JIS K7113. [Comparative Example I-A] 67.5 µl (1.2 mmol) of ethylene glycol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 100 ml (902.4 mmol) of a caprolactone monomer (water content of 150 ppm and an acid value of 0.23 mg-KOH/g) to prepare a polycaprolactone at 180°C, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 73% and 27%, respectively. Number average molecular weight was 49,800 in the polymer. A result of a thermal decomposition test of the polycaprolactone obtained was 82% at 180°C for 6 hours (under a nitrogen stream), 81% at 200°C for 6 hours (under a nitrogen stream), 55% at 180°C for 6 hours (in air), and 42% at 200°C for 6 hours (in air), respectively. Further, in the hydrolizability test, it was 84% at 40°C for 360 hours and 81% at 60°C for 25 hours, respectively. In a sheet having thickness of 75 pm compression-molded from that, degradation ratio according to the above evaluation method for biodegradability was 71% at a period after 25 days, and tensile strength was 252 kgf/cm 2 . [Comparative Example I-B] 67.5 µl (1.2 mmol) of ethylene glycol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 100 ml (902.4 mmol) of a caprolactone monomer (water content of 50 ppm and an acid value of 0.10 mg-KOH/g) to prepare a polycaprolactone at 180°C, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 69% and 31%, respectively. A result of a thermal decomposition test of the polycaprolactone obtained was 88% at 180°C for 6 hours (under a nitrogen stream), 87% at 200°C for 6 hours (under a nitrogen stream), 60% at 180°C for 6 hours (in air), and 48% at 200°C for 6 hours (in air), respectively. Number average molecular weight was 64,000 in the polymer. Further, in the hydrolizability test, it was 92% at 40°C for 360 hours and 91% at 60°C for 25 hours, respectively. In a sheet having thickness of 75 µm compression-molded from that, degradation ratio according to the above evaluation method for biodegradability was 72% at a period after 25 days, and tensile strength was 252 kgf/cm 2 . [Comparative Example I-C] 189.5 µl (1.2 mmol) of octanol (molecular weight of 130.23) which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 100 ml (902.4 mmol) of a caprolactone monomer (molecular weight of 114, water content of 50 ppm and an acid value of 0.10 mg-KOH/g) to prepare a polycaprolactone at 180°C and, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 48% and 25%, respectively, and the remainder was an alkyl terminal derived from octanol. Number average molecular weight was 70,400 in the polymer. A result of a thermal decomposition test of the polycaprolactone obtained was 82% at 180°C for 6 hours (under a nitrogen stream), 95% at 200°C for 6 hours (under a nitrogen stream), 95% at 180°C for 6 hours (in air), and 92% at 200°C for 6 hours (in air), respectively. Further, in the hydrolizability test, it was 99% at 40°C for 360 hours and 98% at 60°C for 25 hours, respectively. In a sheet having thickness of 75 µm compression-molded from that, degradation ratio according to the above evaluation method for biodegradability was 59% at a period after 25 days, and tensile strength was 250 kgf/cm 2 . [Example I-1] 284.2 µl (1.8 mmol) of octanol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 100 ml (902.4 mmol) of a caprolactone monomer (water content of 50 ppm and an acid value of 0.10 mg-KOH/g) to conduct a polymerization at 180°C, followed by allowing to react with 322.6 µl (2. 1 mmol) of hexamethylene diisocyanate which is a modifier to prepare a polycaprolactone and, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 0% and 27%, respectively, and the remainder was an alkyl terminal derived from octanol. Number average molecular weight was 67,400 in the polymer. A result of a thermal decomposition test of the polycaprolactone obtained was 99% at 180°C for 6 hours (under a nitrogen stream), 99% at 200°C for 6 hours (under a nitrogen stream), 98% at 180°C for 6 hours (in air), and 98% at 200°C for 6 hours (in air), respectively. Further, in the hydrolizability test, it was 99% at 40°C for 360 hours and 98% at 60°C for 25 hours, respectively. In a sheet having thickness of 75 pm compression-molded from that, degradation ratio according to the above evaluation method for biodegradability was 47% at a period after 25 days, and tensile strength was 260 kgf/cm 2 . [Example I-2] 284.2 µl (1.8 mmol) of octanol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 100 ml (902.4 mmol) of a caprolactone monomer (water content of 50 ppm and an acid value of 0.10 mg-KOH/g) to conduct a polymerization at 180°C, followed by allowing to react with 86.2 µl (1.0 mmol) of butylene oxide and 322.6 µl (2.1 mmol) of hexamethylene diisocyanate which are a modifier to prepare a polycaprolactone and, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 0%, respectively. Number average molecular weight was 63,800 in the polymer. A result of a thermal decomposition test of the polycaprolactone obtained was 102% at 180°C for 6 hours (under a nitrogen stream), 102% at 200°C for 6 hours (under a nitrogen stream), 100% at 180°C for 6 hours (in air), and 100% at 200°C for 6 hours (in air), respectively. Further, in the hydrolizability test, it was 99% at 40°C for 360 hours and 98% at 60°C for 25 hours, respectively. In a sheet having thickness of 75 µm compression-molded from that, degradation ratio according to the above evaluation method for biodegradability was 38% at a period after 25 days, and tensile strength was 252 kgf/cm 2 . [Example I-3] 245.8 mg (1.2 mmol) of aluminum isopropoxide which is an initiator was added to 100 ml (902.4 mmol) of caprolactone monomer (water content of 50 ppm and an acid value of 0.10 mg-KOH/g) to conduct a polymerization at 180°C, followed by allowing to react with 86.2 µl (1.0 mmol) of butylene oxide and 322.6 µl (2.1 mmol) of hexamethylene diisocyanate which are a modifier to prepare a polycaprolactone and, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 0%, respectively. Number average molecular weight was 37,100 in the polymer. A result of a thermal decomposition test of the polycaprolactone obtained was 100% at 180°C for 6 hours (under a nitrogen stream), 100% at 200°C for 6 hours (under a nitrogen stream), 99% at 180°C for 6 hours (in air), and 99% at 200°C for 6 hours (in air), respectively. Further, in the hydrolizability test, it was 99% at 40°C for 360 hours and 98% at 60°C for 25 hours, respectively. In a sheet having thickness of 75 µm compression-molded from tat, degradation ratio according to the above evaluation method for biodegradability was 45% at a period after 25 days, and tensile strength was 255 kgf/cm 2 . [Comparative Example I-D] 114.2 µl (1.2 mmol) of diethylene glycol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 50 ml (451.2 mmol) of a caprolactone monomer (water content of 150 ppm and an acid value of 0.10 mg-KOH/g) and 65.0 g (451.2 mmol) of a lactide monomer (water content of 70 ppm and an acid value of 0.12 mg-KOH/g) to prepare a (caprolactone/lactide) (50/50) block copolymer at 180°C, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 63% and 37%, respectively. It is to be noted that in the case of a block copolymer, lactide was polymerized after polymerization of caprolactone (hereinafter, in the case of a block copolymer, the same reaction order is applied). Number average molecular weight was 76,400 in the polymer. A result of a thermal decomposition test of samples was 50% at 180°C for 6 hours (under a nitrogen stream), 33% at 200°C for 6 hours (under a nitrogen stream), 31% at 180°C for 6 hours (in air), and 25% at 200°C for 6 hours (in air), respectively. Further, in the hydrolizability test, it was 55% at 40°C for 360 hours and 48% at 60°C for 25 hours, respectively. In a sheet having thickness of 75 pm compression-molded from that, degradation ratio according to the above evaluation method for biodegradability was 58% at a period after 25 days, and tensile strength was 62 kgf/cm 2 . [Comparative Example I-E] 189.5 µl (1.2 mmol) of octanol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 50 ml (451.2 mmol) of a caprolactone monomer (water content of 50 ppm and an acid value of 0.10 mg-KOH/g) and 65.0 g (451.2 mmol) of a lactide monomer (water content of 70 ppm and an acid value of 0.12 mg-KOH/g) to prepare a (caprolactone/lactide) (50/50) block copolymer at 180°C and, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 46% and 29%, respectively. Number average molecular weight was 82,500 in the polymer. A result of a thermal decomposition test of the polycaprolactone obtained was 81% at 180°C for 6 hours (under a nitrogen stream), 77% at 200°C for 6 hours (under a nitrogen stream), 50% at 180°C for 6 hours (in air), and 29% at 200°C for 6 hours (in air), respectively. Further, in the hydrolizability test, it was 77% at 40°C for 360 hours and 69% at 60°C for 25 hours, respectively. In a sheet having thickness of 75 pm compression-molded from that, degradation ratio according to the above evaluation method for biodegradability was 52% at a period after 25 days, and tensile strength was 63 kgf/cm 2 . [Example I-4] 284.2 µl (1.8 mmol) of octanol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 50 ml (451.2 mmol) of a caprolactone monomer (water content of 50 ppm and an acid value of 0.10 mg-KOH/g) and 65.0 g (451.2 mmol) of a lactide monomer (water content of 70 ppm and an acid value of 0.12 mg-KOH/g) to conduct a polymerization at 180°C and, followed by allowing to react with 322.6 µl (2.1 mmol) of hexamethylene diisocyanate which is a modifier to prepare a (caprolactone/lactide) (=50/50) block copolymer and, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 0% and 27%, respectively. Number average molecular weight was 84,000 in the polymer. A result of a thermal decomposition test of the polycaprolactone obtained was 98% at 180°C for 6 hours (under a nitrogen stream), 97% at 200°C for 6 hours (under a nitrogen stream), 89% at 180°C for 6 hours (in air), and 79% at 200°C for 6 hours (in air), respectively. Further, in the hydrolizability test, it was 82% at 40°C for 360 hours and 75% at 60°C for 25 hours, respectively. In a sheet having thickness of 75 pm compression-molded from that, degradation ratio according to the above evaluation method for biodegradability was 39% at a period after 25 days, and tensile strength was 62 kgf/cm 2 . [Example I-5] 284.2 µl (1.8 mmol) of octanol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 50 ml (451.2 mmol) of a caprolactone monomer (water content of 50 ppm and an acid value of 0.10 mg-KOH/g) and 65.0 g (451.2 mmol) of a lactide monomer (water content of 70 ppm and an acid value of 0.12 mg-KOH/g) to conduct a polymerization at 180°C, followed by allowing to react with 86.2 µl (1.0 mmol) of butylene oxide and 322.6 µl (2.1 mmol) of hexamethylene diisocyanate which are a modifier to prepare a (caprolactone/lactide) (=50/50) block copolymer and, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 0%, respectively. Number average molecular weight was 84,200 in the polymer. A result of a thermal decomposition test of the polycaprolactone obtained was 99% at 180°C for 6 hours (under a nitrogen stream), 99% at 200°C for 6 hours (under a nitrogen stream), 98% at 180°C for 6 hours (in air), and 95% at 200°C for 6 hours (in air), respectively. Further, in the hydrolizability test, it was 98% at 40°C for 360 hours and 92% at 60°C for 25 hours, respectively. In a sheet having thickness of 75 pm compression-molded from that, degradation ratio according to the above evaluation method for biodegradability was 31% at a period after 25 days, and tensile strength was 65 kgf/cm 2 . [Comparative Example I-F] 67.5 µl (1.2 mmol) of ethylene glycol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 40 ml (361.0 mmol) of a caprolactone monomer (water content of 50 ppm and an acid value of 0.10 mg-KOH/g) and 78.0 g (541.4 mmol) of a lactide monomer (water content of 70 ppm and an acid value of 0.12 mg-KOH/g) to prepare a (caprolactone/lactide) (=40/60) random copolymer at 180°C, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 72% and 28%, respectively. Number average molecular weight was 87,700 in the polymer. A result of a thermal decomposition test of samples was 89% at 180°C for 6 hours (under a nitrogen stream), 85% at 200°C for 6 hours (under a nitrogen stream), 85% at 180°C for 6 hours (in air), and 85% at 200°C for 6 hours (in air), respectively. Further, in the hydrolizability test, it was 82% at 40°C for 360 hours and 76% at 60°C for 25 hours, respectively. In a sheet having thickness of 75 pm compression-molded from that, degradation ratio according to the above evaluation method for biodegradability was 77% at a period after 25 days, and tensile strength was 71 kgf/cm 2 . [Comparative Example I-G] 189.5 µl (1.2 mmol) of octanol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 40 ml (361.0 mmol) of a caprolactone monomer (water content of 50 ppm and an acid value of 0.10 mg-KOH/g) and 78.0 g (541.4 mmol) of a lactide monomer (water content of 70 ppm and an acid value of 0.12 mg-KOH/g) to prepare a (caprolactone/lactide) (=40/60) random copolymer at 180°C, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 49% and 25%, respectively. Number average molecular weight was 89,100 in the polymer. A result of a thermal decomposition test of samples was 95% at 180°C for 6 hours (under a nitrogen stream), 95% at 200°C for 6 hours (under a nitrogen stream), 91% at 180°C for 6 hours (in air), and 89% at 200 °C for 6 hours (in air), respectively. Further, in the hydrolizability test, it was 92% at 40°C for 360 hours and 87% at 60°C for 25 hours, respectively. In a sheet having thickness of 75 µm compression-molded from that, degradation ratio according to the above evaluation method for biodegradability was 71% at a period after 25 days, and tensile strength was 73 kgf/cm 2 . [Example I-6] 284.2 µl (1.8 mmol) of octanol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 40 ml (361.0 mmol) of a caprolactone monomer (water content of 50 ppm and an acid value of 0.10 mg-KOH/g) and 78.0 g (541.4 mmol) of lactide monomer (water content of 70 ppm and an acid value of 0.12 mg-KOH/g) to conduct a polymerization, followed by allowing to react with 86.2 µl (1.0 mmol) of butylene oxide and 322.6 µl (2.1 mmol) of hexamethylene diisocyanate which are a modifier to obtain a (caprolactone/lactide) (=40/60) random copolymer at 180°C, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 0%, respectively. Number average molecular weight was 89,900 in the polymer. A result of a thermal decomposition test of samples was 100% at 180°C for 6 hours (under a nitrogen stream), 98% at 200°C for 6 hours (under a nitrogen stream), 101% at 180°C for 6 hours (in air), and 97% at 200°C for 6 hours (in air), respectively. Further, in the hydrolizability test, it was 98% at 40°C for 360 hours and 97% at 60°C for 25 hours, respectively. In a sheet having thickness of 75 pm compression-molded from that, degradation ratio according to the above evaluation method for biodegradability was 52% at a period after 25 days, and tensile strength was 73 kgf/cm 2 . [Example I-7] 411.5 µl (1.2 mmol) of titanium butoxide which is an initiator were added to 40 ml (361.0 mmol) of a caprolactone monomer (water content of 50 ppm and an acid value of 0.10 mg-KOH/g) and 78.0 g (541.4 mmol) of lactide monomer (water content of 70 ppm and an acid value of 0.12 mg-KOH/g) to conduct a polymerization at 180°C, followed by allowing to react with 86.2 µl (1.0 mmol) of butylene oxide and 322.6 µl (2.1 mmol) of hexamethylene diisocyanate which are a modifier to obtain a (caprolactone/lactide) (=40/60) random copolymer, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 0%, respectively. A result of a thermal decomposition test of samples was 98% at 180°C for 6 hours (under a nitrogen stream), 98% at 200°C for 6 hours (under a nitrogen stream), 92% at 180°C for 6 hours (in air), and 91% at 200°C for 6 hours (in air), respectively. Number average molecular weight was 35,500 in the polymer. Further, in the hydrolizability test, it was 94% at 40°C for 360 hours and 92% at 60°C for 25 hours, respectively. In a sheet having thickness of 75 pm compression-molded from that, degradation ratio according to the above evaluation method for biodegradability was 54% at a period after 25 days, and tensile strength was 75 kgf/cm 2 . The above results are shown in Table I-1. 1) Results of a thermal decomposition test at 200°C for 6 hours (in air). 2) Results of a hydrolysis test at 60°C and humidity of 80% for 25 hours. Hereinafter, Examples are illustrated in relation to a particle-state composition for agriculture and gardening of the No. II in the present invention. (1) Synthesis of an aliphatic polyester resin employed as a coating thin layer II-A in which terminals are controlled or not controlled. The following substances were employed as raw materials for the synthesis. Caprolactone monomer: molecular weight of 114, water content of 50 ppm (by mass), and an acid value of 0.10 mg-KOH/g. Lactide monomer: molecular weight of 144, water content of 70 ppm (by mass), and an acid value of 0.12 mg-KOH/g. [Comparative Synthesis Example II-1] (Synthesis of an aliphatic polyester resin II-1 in which terminals are not controlled) 67.5 µl (1.2 mmol) of ethylene glycol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 100 ml (902.4 mmol) of a caprolactone monomer to prepare a polycaprolactone at 180°C, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 69% and 31%, respectively. [Comparative Synthesis Example II-2] (Synthesis of an aliphatic polyester resin II-1 in which terminals are controlled) 189.5 µl (1.2 mmol) of octanol (molecular weight of 130.23) which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 100 ml (902.4 mmol) of a caprolactone monomer to synthesize a polycaprolactone at 180°C, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 48% and 25%, respectively, with respect to total terminals, and the remainder was an alkyl terminal derived from octanol. [Synthesis Example II-1] (Synthesis of an aliphatic polyester resin II-2 in which terminals are controlled) 284.2 µl (1.8 mmol) of octanol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 100 ml (902.4 mmol) of a caprolactone monomer (water content of 50 ppm and an acid value of 0.10-KOH/g) to polymerize at 180°C, followed by allowing to react with 322.6 µl (2.1 mmol) of hexamethylene diisocyanate which are a modifier to obtain a polycaprolactone and, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 0% and 27%, respectively. [Synthesis Example II-2] (Synthesis of an aliphatic polyester resin II-3 in which terminals are controlled) 284.2 µl (1.8 mmol) of octanol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 100 ml (902.4 mmol) of a caprolactone monomer (water content of 50 ppm and an acid value of 0.10-KOH/g) to conduct a polymerization at 180°C, followed by allowing to react with 86.2 µl (1.0 mmol) of butylene oxide which is a modifier to obtain a polycaprolactone and, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 0%, respectively. [Synthesis Example II-3] (Synthesis of an aliphatic polyester resin II-4 in which terminals are controlled) 284.2 µl (1.8 mmol) of octanol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 100 ml (902.4 mmol) of a caprolactone monomer to conduct a polymerization at 180°C, followed by allowing to react with 86.2 µl (1.0 mmol) of butylene oxide and 322.6 µl (2.1 mmol) of hexamethylene diisocyanate which are a modifier to obtain a polycaprolactone in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 0%, respectively. [Comparative Synthesis Example II-3] (Synthesis of an aliphatic polyester resin II-2 in which terminals are not controlled) 114.2 µl (1.2 mmol) of diethylene glycol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 50 ml (451.2 mmol) of a caprolactone monomer and 65.0 g (451.2 mmol) of a lactide monomer to synthesize at 180°C. In a block copolymer (polycaprolactone/lactide=50/50) obtained, a proportion occupied by an alcohol terminal and a carboxylic terminal was 63% and 37%, respectively. [Comparative Synthesis Example II-4] (Synthesis of an aliphatic polyester resin II-5 in which terminals are controlled) 284.2 µl (1.8 mmol) of octanol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 50 ml (451.2 mmol) of a caprolactone monomer and 65.0 g (451.2 mmol) of a lactide monomer to synthesize a block copolymer (caprolactone/lactide= 50/50) at 180°C and, in which a proportion occupied by an alcohol terminal and a carboxylic terminal was 46% and 29%, respectively. [Synthesis Example II-4] (Synthesis of an aliphatic polyester resin II-6 in which terminals are controlled) 284.2 µl (1.8 mmol) of octanol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 50 ml (451.2 mmol) of a caprolactone monomer and 65.0 g (451.2 mmol) of a lactide monomer to conduct a polymerization at 180°C, followed by allowing to react with 322.6 µl (2.1 mmol) of hexamethylene diisocyanate which are a modifier. In a block copolymer (caprolactone/lactide= 50/50) obtained, a proportion occupied by an alcohol terminal and a carboxylic terminal was 0% and 27%, respectively. [Synthesis Example II-5] (Synthesis of an aliphatic polyester resin II-7 in which terminals are controlled) 284.2 µl (1.8 mmol) of octanol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 50 ml (451.2 mmol) of a caprolactone monomer and 65.0 g (451.2 mmol) of a lactide monomer to conduct a polymerization at 180°C, followed by allowing to react with 86.2 µl (1.0 mmol) of butylene oxide and 322.6 µl (2.1 mmol) of hexamethylene diisocyanate which are a modifier. In a block copolymer (caprolactone/lactide= 50/50) obtained, a proportion occupied by an alcohol terminal and a carboxylic terminal was 0%, respectively. [Comparative Synthesis Example II-5] (Synthesis of an aliphatic polyester resin II-3 in which terminals are not controlled) 67.5 µl (1.2 mmol) of ethylene glycol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 40 ml (361.0 mmol) of a caprolactone monomer and 50 ml, 78.0 g (541.4 mmol) of a lactide monomer to synthesize at 180°C. In a random copolymer (polycaprolactone/lactide=40/60) obtained, a proportion occupied by an alcohol terminal and a carboxylic terminal was 72% and 28%, respectively. [Comparative Synthesis Example II-6] (Synthesis of an aliphatic polyester resin II-8 in which terminals are controlled) 189.5 µl (1.2 mmol) of octanol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 40 ml (361.0 mmol) of a caprolactone monomer and 78.0 g (541.4 mmol) of a lactide monomer to synthesize at 180°C. In a random copolymer (polycaprolactone/lactide=40/60) obtained, a proportion occupied by an alcohol terminal and a carboxylic terminal was 49% and 25%, respectively. [Synthesis Example II-6] (Synthesis of an aliphatic polyester resin II-9 in which terminals are controlled) 284.2 µl (1.8 mmol) of octanol which is an initiator and 3.4 µl (8.4x10 -3 mmol) of tin octylate which is a catalyst were added to 40 ml (451.2 mmol) of caprolactone monomer and 78.0 g (541.4 mmol) of a lactide monomer to conduct a polymerization at 180°C, followed by allowing to react with 86.2 µl (1.0 mmol) of butylene oxide and 322.6 µl (2.1 mmol) of hexamethylene diisocyanate which are a modifier. In a random copolymer (caprolactone/lactide= 40/60) obtained, a proportion occupied by an alcohol terminal and a carboxylic terminal was 0%, respectively. [Synthesis Example II-7] (Synthesis of an aliphatic polyester resin II-10 in which terminals are controlled) 411.5 µl (1.2 mmol) of titanium butoxide which is an initiator was added to 40 ml (451.2 mmol) of a caprolactone monomer and 78.0 g (541.4 mmol) of a lactide monomer to conduct a polymerization at 180°C, followed by allowing to react with 86.2 µl (1.0 mmol) of butylene oxide which is a modifier. In a random copolymer (caprolactone/lactide= 40/60) obtained, a proportion occupied by an alcohol terminal and a carboxylic terminal was 0%, respectively. (2) Method for the preparation of a particle-state composition for agriculture and gardening, and an apparatus Figure 7 shows an apparatus in a preferred embodiment of the present invention. Blowing column 1 has a column diameter of 200 mm, height of 180 mm, diameter of an opening for blowing air of 42 mm, and which has a hole 2 for throwing a fertilizer and a hole 3 for exhausting a waste gas. Air for blowing is blown from a blower 10, and it reaches the blowing column through an orifice flow meter 9 and a heat exchanger 8. Flow volume is controlled at the flow meter 9, temperature is controlled at the heat exchanger 8, and waste gas is exhausted from the hole 3 for exhausting to an outside of the column. A particle-state fertilizer to be supplied for coating is thrown from the hole 2 for throwing a fertilizer while streaming a fixed heat air to form a blowing stream. Treatment for coating is carried out by spraying the a solution containing a cellulose acetate composition having a low substitution degree through a nozzle 4 for a liquid against the blowing stream after adjusting temperature of particles for coating to a fixed temperature. Preparation of a solution for coating is carried out while agitating in the vicinity of a boiling point of solvent after supplying a fixed amount of a coating material and solvent into a liquid tank 11. The solution for coating is supplied into the nozzle 4 by a pump 5, and keeping warmth is sufficiently conducted in order to maintain a temperature in a system. After supplying the fixed solution for coating, the pump 5 is stopped, and then the blower 10 is stopped. Fertilizer coated is taken out of a hole 7 for taking out. 6 is a valve. In the Figure 7, T 1 , T 2 , and T 3 are a thermometer, and SL is steam. It is to be noted that a particle-state fertilizer was coated while maintain the following basic conditions in all Examples and Comparative Examples. Nozzle for a liquid: opening of 0.8 mm, a Fullcon type Amount of heated air: 4 m 3 /min Temperature of heated air: 100°C Kind of fertilizer: Potassium-ammonium phosphate-nitrate having 5-7 meshes Thrown amount of fertilizer: 5 kg Concentration of a coating solution: Solid content of 5% by weight Feed amount of a coating solution: 0.5 kg/minute Coating period: 10 minutes Coating ratio (based on fertilizer): 5.5% by weight (containing components of surfactants) Solvent: Tetrahydrofran (THF) Coating material II-A: There were employed materials obtained in the above-described Synthesis Examples II-1 to II-7 and Comparative Synthesis Examples II-1 to II-6. Coating material II-B: Diacetate: manufactured by Daicel Chemical Industries, Ltd. [acetylated degree of 55.0 and viscosity of 100 cps in 6%-acetone solution] Coating material II-C: (additives to be added to the Coating material II-A and Coating material II-B): talc (3) Composition of a coating thin layer and biodegradability test Two sides were cut in relation to every particle of 50 particles of coated samples prepared in the Examples and Comparative Examples, and then those were immersed in water to remove internal fertilizing components. After drying, those were finely crushed, and decomposition ratio was measured according to JIS K6950 (an experimental method for biodegradability under airing by an active sludge). Active sludge employed was an active sludge sent from a municipal drainage in Himeji city. [Examples II-1 to II-10 and Comparative Examples II-1 to II-8] Coated phosphorous potassium ammonium nitrate having a variety of composition in a coating layer was prepared by the above-described method for the preparation using coating materials II-A, II-B, and II-C at a proportion shown in Table II-1. Table II-1 shows results of composition ratio in coating layer and biodegradability in the Examples II-1 to II-10 and Comparative Examples II-1 to II-8. In the case of employing the coating materials I I-A, II-B, II-C, as understood from comparison of the Comparative Examples II-1 and II-3 with Examples II-1, II-3, and II-5, biodegradation rate was able to be significantly lowered over a wide range in Examples II-1, II-3, and II-5, compared to Comparative Examples II-1 and II-3. Also in the case of employing the coating materials II-A and II-C, as understood from comparison of the Comparative Examples II-2 and II-4 with Examples II-2, II-4, and II-6, biodegradation rate was able to be significantly lowered over a wide range in Examples II-2, II-4, and II-6, compared to Comparative Examples II-2 and II-4. Further, also in the case of adding II-B and II-C using the random copolymer (caprolactone/lactide=40/60 or 50/50) as the coating material II-A, as understood from comparison of the Comparative Examples II-5 and II-6 with Examples II-7, and II-8, and from comparison of the Comparative Examples II-7 and II-8 with Examples II-9, and II-10, biodegradation rate was able to be significantly lowered over a wide range by the present invention. POSSIBILITY OF UTILIZATION IN INDUSTRY According to the No. I in the present invention, there can become readily designed aliphatic polyesters having a controlled thermal decomposition property, hydrolizability, and biodegradability without affecting to other physical properties, and there is provided a method for the preparation of such the aliphatic polyesters. In the particle-state composition for agriculture and gardening of the No. II in the present invention, biodegradability in a coating thin layer can become appropriately and selectively lowered, a duration period of time a fertilizing effect can be controlled, and the coating thin layer is disintegrated and decomposed by microorganisms in soil after elution of a fertilizer, whereby, it is not remained in soil. Further, it has an effect that residual components disappear after a cultivation period of farm products by disintegration and decomposition of the coating thin layer, and it becomes easy to control a supply of the fertilizer.

Claims: An aliphatic polyester, which is an aliphatic polyester composed of at least one kind of a monomer unit obtainable by ring-opening polymerisation of at least any one of a lactone or a lactide using at least any one of a monohydric alcohol having a high boiling point or a metal alkoxide, wherein a proportion of the number of the alcohol terminals is not more than 50% and/or a proportion of the number of the carboxylic acid terminals is not more than 30% based on the number of total terminals in the aliphatic polyester, said aliphatic polyester having urethane bonds, ether bonds, or amide bonds which are derived from a reaction with a least one modifier selected from an isocyanate compound, a carbodiimide compound, an isocyanurate compound, a Schiff base, or a cyclic ether. An aliphatic polyester claimed in claim 1, wherein a proportion of the number of the alkyl group terminals and/or alkenyl group terminals (herein, the alkyl group and/or alkenyl group is a group having a straight chain, cyclic or branched chain which contain a carbon number of 1-24 pieces) is not less than 30% based on the total terminals in the aliphatic polyester. An aliphatic polyester claimed in any one of claim 1 or 2 wherein there are contained said urethane bonds, ether bonds, or amide bonds produced by allowing to react said modifier with the alcohol terminals and/or carboxylic acid terminals in 0.2-40 pieces on average based on one molecule of a polymer after modifying. An aliphatic ester according to any one of claims 1 to 3, wherein said isocyanate compound is selected from the group consisting of a monoisocyanate, a diisocyanate, and a triisocyanate. An aliphatic ester according to any one of claims 1 to 3, wherein said cyclic ether is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and an epoxide such as styrene oxide. An aliphatic ester according to any one of claims 1 to 5, wherein said cyclic ether and said isocyanate are employed together. An aliphatic ester according to claim 6, wherein the epoxide is added after the completion of a reaction by adding the isocyanate. An aliphatic ester according to claim 1, wherein a ½ molar ratio is added of the diisocyanate to a monofunctional alcohol-terminated aliphatic polyester obtained using a monoalcohol which is an initiator, an aliphatic polyester having alkyl groups at terminals is obtained by connecting through a urethane bond derived from 2 mols of the aliphatic polyesters. An aliphatic ester according to any one of claims 1 to 8, wherein said cyclic ether is butylene oxide. An aliphatic ester according to any one of claims 1 to 8, wherein said isocyanate is hexamethylene diisocyanate. An aliphatic ester according to any one of daims 1 to 10, wherein said cyclic ether is butylene oxide and said isocyanate is hexamethylene diisocyanate. A method for the preparation of an aliphatic polyester by adjusting a proportion of the number of the alcohol terminals to not more than 50% and/or a proportion of the number of the carboxylic acid terminals to not more than 30% based on the number of total terminals, in which at least one kind of a lactone or lactide is polymerized by ring-opening using at least one kind of a monoalcohol having a high boiling point or a metal alkoxide as an initiator, and then allowed to react with at least one modifier selected from an isocyanate compound, a carbodiimide compound, an isocyanurate compound, a Schiff base, or a cyclic ether, in providing urethane bonds, ether bonds or amide bonds. A method for the preparation of an aliphatic polyester claimed in claim 12 wherein there are contained said urethane bonds, ether bonds, or amide bonds produced by allowing to react said modifier to terminals in the aliphatic polyester having said alcohol terminals and/or said carboxylic acid terminals in 0.2-40 pieces on average, based on one molecule of a polymer after modifying. A particle-state composition for agriculture and gardening, characterized in that the surface of a particle-state fertilizer is coated by a coating material II-A alone or a mixture of the coating material II-A with a coating material II-B, the coating material II-A is composed of a terminal-controlled aliphatic polyester as claimed in any one of claims 1-11, and the coating material II-B is composed of at least one kind selected from the group consisting of an olefin polymer, a copolymer containing an olefin, a vinylidene chloride polymer, a copolymer containing vinylidene chloride, a diene-based polymer, waxes, a petroleum resin, a natural resin, a cellulose acetate resin, a polycaprolactone and oils and fats, and a hydrogenated oil, a solid fatty acid, and metal salts of fatty adds. A particle-state composition for agriculture and gardening claimed in daim 14, wherein the coating material II-B is a polycaprolactone, a cellulose acetate, or a mixture thereof. A particle-state composition for agriculture and gardening claimed in claim 14 or 15, wherein there are further added inorganic fillers and/or additives for resins. A particle-state composition for agriculture and gardening claimed in claim 16, wherein the inorganic fillers are talc, calcium carbonate, or a mixture thereof.

Inventors: KAJIKAWA YASUTERU, SAKANE MASANORI, TANIGAWA MICHIYO, KAJIKAWA, YASUTERU, SAKANE, MASANORI, TANIGAWA, MICHIYO
Applicants: DAICEL CHEM, DAICEL CHEMICAL INDUSTRIES, LTD.
Application year: 1999
Main classification: C08G63
IPC codes: C08G18, C08G63, C09D175, C09D167