JPH11116950A - Formed item and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a formed item having biodegradability, water retention property and sustained release of a chemical by using a polyamion acid, especially a crosslinked polyamino acid. SOLUTION: A polyamino acid has a fundamental structure of a polypeptide produced by a dehydration condensation of amino acids such as 20 kinds of essential amino acids. An α-amino acid contained may be optically active or racemic. The polyamino acid may be a copolymer including a monomer other than the amino acids, for example, an aminocarboxylic acid, an aminosulfonic acid, etc. A polyaspartic acid and glutamic acid are preferably employed as a fundamental structure-forming acid. The polyamino acid is preferably produced by ring-opening and crosslinking of a part of a polysuccinimde with a polyamine and then hydrolyzing the product with an alkali or by introducing a water- absorbent substituent. The formed item is manufactured by means of a compression granulation, for example tabulating, briquetting and compacting of crushing a formed item.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a molded article having biodegradability. More specifically, the present invention relates to a molded article containing a polyamino acid having biodegradability, which is useful for agricultural and horticultural use, pharmaceutical use, and the like. More specifically, the present invention relates to a molded product made of a polyamino acid that is biodegradable and has both water retention and chemical sustained release properties and is environmentally friendly.

[0002]

[Prior art]

[Growing of plants] The growing of plants, including the raising of seedlings, is difficult to manage, and many methods have been used. However, a great deal of labor and cost were required for comprehensive management. The key factors in its management are irrigation management, pesticides,
Donation of active ingredients to plants such as fertilizers. In other words, in order to achieve good growth of useful plants, during the growth period, the solid phase in the soil, liquid phase, maintaining the balance of the three phases of the gas phase,
It is indispensable conditions to keep the soil at an appropriate level of water, to keep the plant hydrated, and to provide an appropriate amount of the active ingredient at the appropriate time. For this purpose, a method of imparting water retention to soil and a method of sustained release of an active ingredient have been widely used. As a method of giving water retention to soil,
It is widely practiced to mix a soil improving material having a water retaining property (hereinafter referred to as a water retaining material) into soil.

[0003] In addition to the water retention effect, the water retention material is required to have a ventilation effect for maintaining air circulation in order to maintain root respiration and suppress root rot. Specific examples of the water retention material include, for example, mulch, Kanuma soil, peat moss, perlite, vermiculite, urethane foam, and the like, but they do not always satisfy both the water retention effect and the ventilation effect at the same time. On the other hand, as a method of applying an active ingredient to a plant, there are a method of spraying the active ingredient from the air and a method of spraying an aqueous solution or a water suspension, but the effect is temporary and the effect is not maintained. In order to maintain the effect, the frequency of spraying increases, and a great deal of labor is required. In addition, since it is difficult to spray the medicine uniformly, there is a possibility that a large amount of medicine may be accumulated in an unnecessary part or locally.

On the other hand, as a method for sustained release of an active ingredient, a method has been proposed in which various drugs are granulated to form granules. However, conventional moldings have been formed by mixing a disintegrant and molding the active ingredient by utilizing the disintegration property. However, conventional disintegrants disintegrate gradually over time by utilizing the action of dissolution or elution, etc., so that the diffusion of the internal active ingredient is not sufficient, resulting in absorption of the active ingredient and the like. Was sometimes insufficient. In particular, when used in soil, diffusion of the active ingredient was very difficult.

[Greening of artificial ground] On the other hand, in order to express a comfortable living environment for human beings, green has been introduced into artificial spaces. For example, greening of indoor foliage plants, roads, and side zones of the median strip, planting of street trees, transplanting to artificial ground soil such as coastal sabo forests, and the like have been implemented. However, these artificially created environments are largely unsuitable for plant growth and do not grow well due to poor root growth or insufficient root viability. , Often die. To prevent this, a great deal of effort is required, and often it does not always work. This is often due to poor water and poor plant management, especially in such environments.
There has been a demand for an appropriate material that can easily control irrigation and the active ingredient. Furthermore, it is necessary to activate the growth of roots in order to prevent such death and the like, and a material that activates roots and has water retention properties has been desired.

[Water Retaining Material Using Water Absorbent Resin] On the other hand, it is well known that a highly water absorbent resin that absorbs water several hundred times its own weight is mixed with soil to improve the water retention of soil. In particular, it is expected to play an important role in environmental protection such as desert greening and desertification prevention. Specific examples of these superabsorbent resins include, for example, partially neutralized cross-linked polyacrylic acid (JP-A-55-84304, U.S. Pat. No. 4,625,001), and a partially hydrolyzed starch-acrylonitrile copolymer (JP-A No. 4-2,001). No. 46-43995), a starch-acrylic acid graft copolymer (JP-A-51-1254).
No. 68), a hydrolyzate of a vinyl acetate-acrylic acid ester copolymer (JP-A-52-14689), and a copolymerized cross-linked product of 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid (European Patent 0068189) ), A crosslinked product of a cationic monomer (US Pat. No. 4,906,717),
Crosslinked isobutylene-maleic anhydride copolymers (U.S. Pat. No. 4,389,513) and crosslinked polyethylene oxides (JP-A-6-157795, etc.) are known.

[0007] Examples of the use thereof include, for example, a soil conditioner formed into granules containing an acidity correcting material, a water-absorbing polymer compound and, if necessary, a binder (Japanese Patent Laid-Open No. 2-77).
No. 487), polystyrene expanded particles, superabsorbent resin fine powder, crushed stone powder or sand are kneaded with a water-emulsion-based adhesive or binder to form a granular mass, and then dried soil improver (Japanese Patent Application Laid-Open No. No. 88074), and a granulated product obtained by compression-molding a super water-absorbent resin and a molding aid and having an external coating layer containing the active ingredient from the compression-molded product (Japanese Patent Application Laid-Open No. 7-33644).

However, all of these superabsorbent resins have no biodegradability, and thus have a problem that they remain in soil for a long period of time. For example, when using a cross-linked polyacrylic resin as a water retention material for agriculture and horticulture,
It has been reported that it forms a complex with polyvalent ions such as Ca ^{2+ in} soil and forms an insoluble layer (Matsumoto et al.
Polymer, Vol. 42, August, 1993). It is said that such a layer has a possibility of preventing salt damage in an arid land having a high salt concentration. However, such layers are completely absent in nature and will accumulate underground over long periods of use. Although the substance itself is said to be harmless, the effects of long-term accumulation on ecosystems are unknown, need to be thoroughly investigated, and the effects on the global environment are questionable.
In the case of a nonionic water-absorbing resin, a complex is not formed, but it is expected to accumulate in soil due to non-decomposability. Furthermore, these polymerization resins use monomers such as acrylic acid, which are highly toxic to plants, as raw materials, and many studies have been made to remove them from products after polymerization. It is difficult to completely remove them, and there is a possibility that lignification of the leaves of the plant or growth inhibition may be caused.

[Polyamino acid] Polyamino acid is known as a polymer having characteristics such as safety and biodegradability due to its chemical structure. In addition to being studied as a biopolymer model for a long time, polyamino acid is also used as artificial leather. Also, research on the use of such as pharmaceutical carriers and cosmetics has been conducted. EP 94/09628 discloses that polyamino acids such as polyaspartic acid and its copolymers promote fertilizer uptake by plants and promote plant growth. However, since the polyamino acid itself is water-soluble, it has been difficult for the polyamino acid to flow out in the soil by irrigation or the like and to maintain its effect. Then, the present inventors have developed a seedling raising soil composition used in a seedling raising pot (Japanese Patent Application No. Hei 7-171470).
issue). Although this composition is extremely significant in that it has an effect of promoting root survival of plants, there is still room for improvement in controlling the sustained release of the active ingredient. That is, a material that has biodegradability, does not accumulate in soil, has a high effect as a water retention material, and can further control the sustained release of the active ingredient has been strongly desired.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a molded article having both biodegradability, water retention, and sustained release of a drug which solves the above-mentioned problems. is there. More specifically, the present invention relates to a molded article that decomposes after use, has no accumulation property in soil, has excellent water retention, and has a sustained release of chemicals, thereby promoting the growth of plant roots, leaves and the like. is there.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the use of a molded article containing a polyamino acid, particularly a crosslinked polyamino acid, can achieve the above object. The present invention has been completed. That is, the present invention is a molded article comprising a polyamino acid. The present invention is specified by the following items [1] to [25].

[1] A molded article containing a polyamino acid. [2] In addition to the polyamino acid, a binder, and / or
Alternatively, a molded article comprising a resin composition containing a biologically active component. [3] The molded article according to [2], wherein the binder contains a binder resin and / or a clay. [4] the binder resin is a biodegradable resin,
The molded article according to [3]. [5] the biodegradable resin is an aliphatic polyester;
The molded article according to [4].

[6] The molded article according to [5], wherein the aliphatic polyester is polylactic acid. [7] the binder contains an adhesive;
The molded article according to [2]. [8] the biologically active ingredient contains a pesticide;
The molded article according to any one of [1] to [7]. [9] the biologically active ingredient contains a fertilizer;
The molded article according to any one of [1] to [7]. [10] The molded article according to any one of [1] to [9], wherein the polyamino acid is partially crosslinked.

[11] The molded article according to any one of [1] to [10], wherein the polyamino acid is an acidic polyamino acid. [12] The molded article according to any one of [1] to [11], wherein the polyamino acid is polyaspartic acid. [13] The molded article according to any one of [1] to [12], wherein the molded article is a granular molded article. [14] The molded article according to any one of [1] to [12], wherein the molded article is a tablet-shaped molded article. [15] The molded article according to any one of [1] to [12], wherein the molded article is a sheet-shaped molded article.

[16] The method for producing a molded article according to any one of [1] to [15], which comprises compression molding. [17] tabletting;
The method for producing a molded article according to any one of [1] to [15]. [18] briquetting,
The method for producing a molded article according to any one of [1] to [15]. [19] characterized by compacting;
The method for producing a molded article according to any one of [1] to [15]. [20] The molded product obtained by compression molding is moistened and further dried, [1] to [1].
5] The method for producing a molded article according to any one of [1] to [5].

[21] The method for producing a molded article according to any one of [1] to [15], wherein a binder and a polyamino acid are mixed and molded. [22] The method for producing a molded article according to any one of [1] to [15], wherein a thermoplastic resin is used as a binder resin and the mixture is heated and melted. [23] A solution of a binder resin and a polyamino acid are mixed, and the solvent is removed.
5] The method for producing a molded article according to any one of [1] to [5]. [24] A soil composition containing the molded article according to any one of [1] to [15]. [25] A soil improvement method, comprising applying the molded article according to any one of [1] to [15] to soil.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. (1) Structure of polyamino acid The basic skeleton of the polyamino acid used in the present invention is composed of a polypeptide obtained by dehydrating and condensing amino acids. Specific examples of the amino acid component include, for example, 20 kinds of essential amino acids,
L-ornithine, a series of α-amino acids, β-alanine,
amino acids and amino acid derivatives such as γ-aminobutyric acid, neutral amino acids, acidic amino acids, ω-esters of acidic amino acids, basic amino acids, N-substituted basic amino acids, aspartic acid-L-phenylalanine dimer (aspartame); Examples thereof include aminosulfonic acids such as L-cysteic acid. α-amino acid is an optically active form (L-form,
D-form) or a racemic form. Further, the polyamino acid may be a copolymer containing another monomer component.

Examples of the monomer components of the copolymer include aminocarboxylic acid, aminosulfonic acid, aminophosphonic acid,
Examples thereof include hydroxycarboxylic acid, mercaptocarboxylic acid, mercaptosulfonic acid, and mercaptophosphonic acid. Further, polyamines, polyhydric alcohols, polythiols, polycarboxylic acids, polysulfonic acids, polyphosphonic acids, polyhydrazine compounds, polycarbamoyl compounds,
Polyvalent sulfonamide compound, polyvalent phosphonamide compound, polyvalent epoxy compound, polyvalent isocyanate compound,
Examples include a polyvalent isothiocyanate compound, a polyvalent aziridine compound, a polyvalent carbamate compound, a polyvalent carbamic acid compound, a polyvalent oxazoline compound, a polyvalent reactive unsaturated bond compound, and a polyvalent metal. When it is a copolymer, it may be a block copolymer or a random copolymer. Also, it may be a graft. Among these, it is preferable to use polyaspartic acid and glutamic acid having high water absorption as the basic skeleton, and polyaspartic acid suitable for industrial production is particularly preferable.

The side chain structure of the polyamino acid used in the present invention is a group in which an imide ring is simply opened and has a carboxyl group, but other substituents may be introduced. For example, there are amino acid residues such as lysine, a hydrocarbon group having a carboxyl group, and a hydrocarbon group having a sulfonic acid group. In the case of an aspartic acid residue, the carboxyl group or side chain group may be substituted at the α-position or β-position with respect to the amide bond of the polymer main chain, and may be substituted at the β-position. In the case of a group, it may be substituted at the α-position or at the γ-position. The bonding portion between the basic skeleton and the side chain portion of the polyamino acid of the present invention is an amide bond, an ester bond, or a thioester bond.

In the case of a carboxyl group, a salt may be formed even when a hydrogen atom is bonded. Examples of the counter ion of the carboxyl group include alkali metal salts, ammonium salts, and amine salts. The polyamino acid used in the present invention may or may not be crosslinked, but is preferably crosslinked. The bonding portion between the basic skeleton and the crosslinked portion of the present invention is an amide bond, an ester bond, or a thioester bond. These crosslinking portions and side chain portions may be unsubstituted or substituted. As the substituent, an optionally branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group, an optionally substituted phenyl group, or an optionally substituted A naphthyl group, an optionally branched alkoxy group having 1 to 18 carbon atoms, an aralkyloxy group, a phenylthio group, an optionally branched alkylthio group having 1 to 18 carbon atoms,
C1 to C18 optionally branched alkylamino group, C1 to C18 optionally branched dialkylamino group, C1 to C18 optionally branched trialkylammonium Groups, a hydroxyl group, an amino group, a mercapto group, a sulfonyl group, a sulfonic acid group, a phosphonic acid group and salts thereof, an alkoxycarbonyl group, an alkylcarbonyloxy group and the like.

(2) Method for producing polyamino acid Among the polyamino acids used in the present invention, cross-linked polyamino acids are described in JP-A-7-224163, Journal of Polymers,
Vol. 0, No. 10, p. 755 (1993), U.S. Pat.
No. 48863; Japanese Patent Publication No. 52-41309;
279416, JP-T-6-506244; U.S. Pat. Nos. 5,247,068 and 5,284,936, and JP-A-7-309943, but they can be easily produced. Not enough
There is a need for a way to enhance these performances. For example, a method for purifying a water-absorbing polymer as described in Japanese Patent Application No. 9-68186, Japanese Patent Application No. 9-102083 and Japanese Patent Application No. 9-68186.
Japanese Patent Application No. Hei 10-2084 discloses a method for enhancing water absorption by controlling a crosslinking reaction in a production process as described in Japanese Patent Application No. 102084.
-68185, a method of increasing water absorption by increasing the efficiency of a hydrolysis reaction in a production process, a method of introducing a glycino group described in Japanese Patent Application No. 9-16991, and increasing a water absorption capability, There is a method described in Japanese Patent Application No. 7-107773, in which a carboxyl group is introduced to increase water absorbing ability, and a method described in Japanese Patent Application No. 7-107772, in which a sulfonyl group is introduced to increase water absorbing ability, and the like. That is, a method is preferred in which the polysuccinimide is partially ring-opened and crosslinked with a polyamine and then hydrolyzed with an alkali or a substituent capable of exhibiting a water absorbing ability is introduced.

(3) Composition of molded article containing polyamino acid The molded article of the present invention may contain various useful components as necessary. For example, moisture, organic fertilizer, biological fertilizer, chemical fertilizer, compost, chicken dung, organic material, pH adjuster, surfactant, foaming agent, corrosive substance, water retention and fertilizer improvement mineral substance powder (bentonite, zeolite powder, etc.) ), Pesticides (pesticides,
Fungicides, herbicides, fungicides, etc.), plant revitalizers, plant life-promoting agents, insect and animal repellents, soil penetrants, trace element nutrients, diatomaceous earth, clay, lime, plant hormones, minerals, coral sand , Activated carbon, calcium carbonate, magnesium carbonate, kaolin, clay, alumina, silica, titanium oxide, talc, diatomaceous earth, mica, inorganic particles such as shirasu balloon, glass beads, synthetic resin pellets, beads, coarse particles, wood Examples include small pieces, sawdust, cereal flour, crushed plant shells and stems, plant seeds, and useful fungi.
Further, finely radioactive minerals such as Ferguson, far-infrared radiation ceramics, and ethylene gas-absorbing minerals such as Oyaishi and zeolite may be added. Further, an inorganic water retention material such as pearlite, pumice, vermiculite and the like may be added. If necessary, two or more of them can be used in combination.

Examples of the fertilizer used in the present invention are not particularly limited.
It depends on the type of soil, growth conditions, etc. Specific examples of the fertilizer used in the present invention include, for example, “12996 Chemical Products (Chemical Kogyo Nippo, 3 Nihonbashihamacho, Chuo-ku, Tokyo)
-16-8), issued on January 24, 1996), ISBN
4-87326-204-6 C3543].
Ammonia, carbide and chemical fertilizers (pages 1 to 24) "
And compounds having a use as a fertilizer, mixtures thereof, chemical fertilizers, chemical fertilizers, ordinary chemical fertilizers, and compound fertilizers. All of those descriptions are made a part of the disclosure of the present application specification by explicitly citing the cited documents and the cited ranges, and by referring to the explicitly cited ranges, the matters or disclosures described in the present application specification are considered. Matters or disclosures that can be directly and uniquely derived by those skilled in the art.

Examples thereof include ammonium sulfate, urea, lime nitrogen,
Salt and salt, salt and nitrate, molten potassium, potassium sulfate, potassium chloride, potassium nitrate, potassium bicarbonate, monophosphate, diphosphate, lime superphosphate,
There are fertilizer components such as heavy stone, excess stone, slaked lime, quicklime, molten phosphorus, heavy phosphorus, calcined phosphorus, magnesium sulfate, water mug, charcoal mug, silicic acid, charcoal, etc. CDU, U
F, mouldite, mixed phosphorus manure, borate fertilizer, fish manure, vegetable oil cake, organic manure, ordinary chemical, urea-containing sulfurated ammonium phosphate, IB
Phosphorus phosphoric acid, phosphoric acid nitrate potassium, sulfuric acid phosphoric acid containing urea, IB
CDU Phosphorus, Phosphorus chloride, Phosphorous ammonium salt, Phosphorus ammonium salt, Phosphorus acid salt, Phosphorus acid salt, Phosphorus acid salt, Phosphorus acid salt, Phosphorus acid salt, Magnesium sulfurate phosphorus, Urea phosphoric acid Cheap,
Magnesium urea sulfurated phosphorus, nitric acid phosphorus enhanced, urea sulfurated phosphorus enhanced, salted ammonium phosphated, urea phosphorus enhanced magnesium containing urea phosphorus, phosphoric acid masonry, etc., NK Chemicals, advanced phosphate nitrate-based advanced chemicals, phosphorous ammonium nitrate Potassium advanced chemical conversion, chemical fertilizer containing organic, chemical conversion containing Mg, coating fertilizer and the like. These are necessary,
Two or more types can be used in combination. The form is not particularly limited, and examples thereof include granules, powders, and aqueous solutions.

Examples of the pesticides used in the present invention are not particularly limited.
It depends on the type of soil, growth conditions, etc. Specific examples of the pesticides used in the present invention include, for example, “Chemical products of 12996 (Chemical Kogyo Nippo Co., Ltd.
-16-8), issued on January 24, 1996), ISBN
4-87326-204-6 C3543.
No. 8, pesticides (pp. 1463-1575), compounds having a use as pesticides, mixtures thereof, and compositions thereof. All of those descriptions are made a part of the disclosure of the present application specification by explicitly citing the cited documents and the cited ranges, and by referring to the explicitly cited ranges, the matters or disclosures described in the present application specification are considered. Matters or disclosures that can be directly and uniquely derived by those skilled in the art.

Examples include PCP granules, PCP mixed granules, 2.4PA granules, 2.4PA mixed granules, MCP granules, MCC-MCP granules, MCPB granules, MCPCA granules, CNP granules. Agent, CNP-MCP granules, DBN granules, C
AT granules, promethrin granules, promethrin-MCPB
Granules, simetryn granules, simethrin mixed granules, trifluralin granules, benthiocarb granules, benthiocarb-simetrine granules, benthiocarb-CNP granules, NIP granules, NIP-MCP granules, molinate-simetrin granules, chloric acid Herbicides such as salts, granules of dimethoate, granules of ethylthiomethone, granules of mixed ethylthiomethone, granules of DEP, MPP, granules of diazinon, granules of mixed diazinon, cartap granules, granules of cartap, clofenamidine granules , Insecticides such as clofenamidine mixed granules,
Nematocides such as DCIP granules and DBCP granules; and bactericides such as IBP granules. If necessary, two or more of them can be used in combination. Examples of useful cells used in the present invention include VA mycorrhizal fungi, rhizobia, Pseudomonas, Bacillus, and the like.

Examples of the antimicrobial agent used in the present invention include captan, gliodin, benate, thiobendazole, amicar, biocide, kasugamycin,
Griseofulvin, polyoxin and the like.

Examples of plant hormones include auxins such as 2,4-dichlorophenoxyacetic acid, naphthaleneacetic acid and indoleacetic acid which promote rooting and callus formation, kinetin, zeatin, impentenyladenine and benzyl which promote bud differentiation. Cytokinins such as adenine; Other examples include gibberellin, which promotes the growth of stems and leaves, abscisic acid, which has a growth balance regulating action, and ethylene, which promotes flowering and fruit ripening. The required hormones also depend on the type of plant. These may be used alone or in combination of two or more.

Examples of minerals used in the present invention include calcium, magnesium, lithium, strontium, barium, aluminum and the like, but are not particularly limited to carbonates, sulfates, acetates, nitrates, oxalates, and the like.
It is used in the form of phosphate, hydroxide, chloride, bromide, iodide and the like.

The molded article of the present invention may contain a surfactant or a soil penetrant. The surfactant or the soil penetrant is not particularly limited, and examples thereof include sodium lauryl sulfate, triethanolamine lauryl sulfate, and alkyl sulfates such as ammonium lauryl sulfate.
Sodium polyoxyethylene lauryl ether sulfate,
Polyoxyethylene alkyl ether sulfates such as polyoxyethylene lauryl ether triethanolamine sulfate, and alkyl sulfones such as sodium lauryl sulfonate, potassium lauryl sulfonate, triethanolamine lauryl sulfonate, ammonium lauryl sulfonate, and sodium stearyl sulfonate. Acid salts, alkyl diphenyl ether disulfonates such as sodium dodecyl diphenyl ether disulfonate, alkyl aryl sulfonates such as sodium dodecyl benzene sulfonate, sodium dodecyl naphthalene sulfonate, alkyl naphthalene such as sodium salt of β-naphthalene sulfonate formalin condensate Sulfonic acid, lignin sulfonate, sodium distearyl sulfosuccinate, dioctyl sulfo Dialkyl sulfosuccinates such as sodium succinate, polyoxyethylene lauryl ether acetic acid, polyoxyethylene alkyl ether acetates such as sodium polyoxyethylene lauryl ether acetate, and copolymers having a carboxyl group such as an alkylene maleic acid copolymer. Alkali metal salts, coconut oil fatty acids,
Palmitic acid, behenic acid, lauric acid, stearic acid, myristic acid, oleic acid, sodium laurate, potassium laurate, triethanolamine laurate, ammonium laurate, sodium stearate, potassium stearate, triethanolamine stearate, Fatty acids such as ammonium stearate or salts thereof, anionic surfactants such as sodium lauryl phosphate, triethanolamine lauryl phosphate, monoalkyl phosphates such as ammonium lauryl phosphate, lauryl alcohol, myristyl alcohol, cetanol, set Stearyl alcohol, stearyl alcohol, 2-octyldodecanol, higher alcohols such as behenyl alcohol, glycerin, ethylene glycol, diethylene glycol, Triethylene glycol,
Polyhydric alcohols such as polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, sorbitol, sorbitan, pentaerythritol, polyoxyethylene lauryl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl Dodecyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl phenyl ether such as polyoxyethylene nonyl phenyl ether, polyoxyethylene styryl phenyl ether, polyethylene glycol monostearate, polyethylene glycol distearate, ethylene glycol distearate, poly Polyoxyethylene such as oxyethylene hydrogenated castor oil Alkyl esters, copolymers of polyoxyethylene glycol and polyoxypropylene glycol such as polyoxyethylene polyoxypropylene glycol, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan monopalmitate, sorbitan sesquioleate, Sorbitan coconut fatty acid, sorbitan monopalmitate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, etc., polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monococolate fatty acid sorbitan, polypolypalmitate Oxyethylene sorbitan, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, Polyoxyethylene sorbitan alkyl esters such as polyoxyethylene sorbitan oleate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan triisostearate; tetrafatty acid polyoxyethylene sorbite such as polyoxyethylene sorbite tetraoleate; monostearic acid Glycerin alkyl esters such as glycerin, glyceryl monooleate and glyceryl monocaprylate; propylene glycol alkyl esters such as propylene glycol monostearate; polyoxyethylene alkylamines such as polyoxyethylene stearylamine; palm kernel oil fatty acid diethanolamide; laurin Nonionic surfactants such as alkyl alkanolamides such as acid diethanolamide, coconut amide Alkylamine salts such as acetate, stearylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, alkyltrimethylammonium salts such as cetyltrimethylammonium chloride, distearyldimethylammonium chloride,
Dialkyl dimethyl ammonium salts such as dialkyl (12-18) dimethyl ammonium chloride, cationic surfactants such as benzalkonium chloride such as benzalkonium chloride, alkyl betaines such as lauryl betaine and stearyl betaine, and lauryl dimethylamino acetate betaine; Alkyl dimethylamino acetate betaines such as stearyl dimethyl amino acetate betaine, alkyl carboxymethyl hydroxyethyl imidazolinium betaines such as 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, amide amide propyl betaine, cocoate Alkylamidopropyl betaine such as amidopropyl betaine, alkylhydroxysulfobetaine such as laurylhydroxysulfobetaine, lauryldimethylamine Such amphoteric surfactants such as alkyl dimethyl amine oxides such as Sid can be mentioned. It is preferable that these additives have biodegradability from the viewpoint of environmental protection.

Further, in order to form a molded article, to disintegrate the molded article, and to improve the stability and handling of the molded article, a carrier, a disintegrant, an excipient, a molding aid, a bulking agent, etc. , Lubricants, reinforcing agents, plasticizers, dispersants, wetting agents, lubricants, coloring agents, foaming agents, defoamers, antistatic agents, charge control agents, fragrances, stabilizers, buffers, water repellents ,desiccant,
It may contain a water-soluble carrier, a mineral carrier, a solvent and the like. These may be used in combination of two or more as necessary.

[0032] The carrier used in the present invention is not particularly limited, and examples thereof include limestone clay, kaolin, sericite, ziglite, talc, bentonite, acid clay, calcium carbonate, silica, silica sand, diatomaceous earth, and the like. pumice,
Zeolite, perlite, vermiculite, slaked lime,
Urea, ammonium sulfate, salt ammonium, chemical fertilizer, plastic foam,
Examples include slag, fly ash, bran, bran, rice husk, sawdust, wood flour, pulp floc, soy flour, corn stalk, nut hull, fruit nucleus, and the like.

The disintegrating agent used in the present invention is not particularly limited. For example, those used for medicine include agar, starch, hydroxypropyl starch, sodium alginate, carboxymethyl starch ether, gum arabic, tragacanth, Gelatin, casein, cellulose,
Carboxymethylcellulose, carboxymethylcellulose calcium, tween, pluronic, sodium laurate, carboxyl resin, etc., for agricultural and horticultural use, ammonium sulfate, potassium chloride, salt, bentonite, urea, anionic surfactant, for food, salt , Sodium glutamate, sodium inosinate, dextrin, starch, agar and the like.

The molding aid used in the present invention is not particularly limited, but includes lactose, glucose, sucrose, corn starch, wheat, potato starch, calcium carbonate, calcium sulfate, calcium phosphate, mannyl, kaolin,
Sericite, ziglite, talc, acid clay, pumice,
Silica sand, pyroxene, vermiculite, zeolite, perlite, vermiculite, slaked lime, plastic foam, ammonium sulfate, urea, salty ash, slag, fly ash, bran, rice hull, wood flour, soy flour, corn stalk, fruit nucleus, Red clay,
Arabic gum, tragacanth gum, yaraya gum, dextrin, gelatin, methylcellulose, carboxymethylcellulose, sodium glutamate, salt, alumina, silica gel, diatomaceous earth, talc, mica, asbestos, graphite, barium sulfate, silicic anhydride, pulp, dried clay (kibushi Clay, frog-eye clay, bentonite) and the like.

The molded article used in the present invention may be, if necessary,
A water-absorbing resin other than the crosslinked polyamino acid-based resin may be mixed and used. Further, the molded article of the present invention may use a binder. Examples of binders include fully fermented oil residues, clay, gelatin, gum arabic, acacia powder, polyvinylpyrrolidone, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, dextrin, starch, sodium alginate, acrylate latex, Styrene butadiene type latex, vinyl acetate type latex, acrylic acid-acrylamide propane sulfonamide-copolymer, partially saponified polyvinyl alcohol, dioctyl phthalate, and the like.
These binders preferably have biodegradability from the viewpoint of environmental protection.

(4) Method for Preparing Molded Article Containing Polyamino Acid The method for preparing a molded article containing a polyamino acid-based resin is not particularly limited, but typical examples include (4-1) compression granulation and (4) -2) There is a method of molding using a binder, and as a secondary treatment of (4-1), (4-1-1) a molded body obtained by compression molding is moistened and further dried. (4-2) is further divided into (4-2)
-1) There is a method in which a thermoplastic resin is used as a binder, the resin is melted by heating, and the resin is cooled to be molded. These will be described separately. In addition, these adjustment methods are not particularly limited, and a granulation handbook (Ohmsha, Showa 50
Yearly published, edited by the Japan Powder Industry Association). All of those descriptions are made a part of the disclosure of the present application specification by explicitly citing the cited documents and the cited ranges, and by referring to the explicitly cited ranges, the matters or disclosures described in the present application specification are considered. Matters or disclosures that can be directly and uniquely derived by those skilled in the art.

(4-1) Compression Granulation The compact of the present invention is produced by compression granulation. The compression granulation method is not particularly limited, and examples thereof include tableting, briquetting, and compacting of a molded product obtained by the method.

The shape of the obtained compression molded body is not particularly limited, and may be selected as needed. Examples of the shape include, but are not limited to, round, football, triangular, square, rectangular, hexagonal, and ring types, and the plane is a goishi type, a flat type edge, a flat type. , Convex type, concave type, ring type and the like. Briquetting includes sheet, plate, pillow, lens, almond, prism, rod, corrugated sheet, and the like. The compacting may be in a crushed state or the like. The size of the molded article of the present invention is not particularly limited and can be selected according to the intended use. The particle size of the raw material used for tableting and briquetting used in the present invention is not particularly limited, and varies depending on the polyamino acid used and other materials such as additives. Generally, a powder having a wider particle size distribution, such as a mixture of coarse particles and fine particles, provides a stronger molded body. In the case of powder composed of fine particles, it is preferable to mix coarse particles with the raw material powder in order to prevent laminating.

On the other hand, in order to be able to easily supply a constant amount of the raw material powder into the mortar, to maintain the size of the obtained compact and to increase the productivity, it is necessary that there is no variation in density. Preferably, for this purpose, in some cases, it is preferable to sieve the raw material powder to make the particle size uniform or to adjust the particle size by performing a granulation operation in a previous stage. The tableting and briquetting of the present invention may optionally include a plasticizer. If a powder having plasticity is used, plastic deformation is easily caused by compression, the adhesion surface between particles is enlarged, and even after removing the compressive force, no elastic strain remains in the molded body, so that a strong molded body can be formed. It is preferable because it can be obtained. The surface of the raw material powder used in the present invention is steam,
It is preferable not to be contaminated by a gas, an oxide film or the like. For this reason, it is preferable to pulverize the particles just before molding to form a clean fractured surface and form the molded product because a strong molded product can be obtained.

In the tabletting and briquetting of the present invention, a binder may be added in some cases.
The use of a binder facilitates molding when there is a large amount of a hard ore or a porous powder such as coke as a component other than the polyamino acid. Examples of binders include clay, asphalt, portland cement, wax, paraffin, sugar, starch, gilsonite, matrix-type binders such as coal tar pitch, water, molasses, pulp waste liquor, sodium silicate, starch , Pitch emulsion, polyvinyl alcohol, film binders such as bentonite, and reactive binders that form a chemical bond between the binder components or between the binder and other raw material powders. Can be

When the raw material powder used for tableting and briquetting of the present invention contains two or more components,
It is preferable that mixing is sufficiently performed before compression molding. The equipment used for the mixing is not particularly limited, and examples thereof include an edge runner mill and an Erich mixer.

The tableting and briquetting of the present invention may optionally include a lubricant.
The use of a lubricant reduces the internal friction and wall friction inside the powder, improves the transmission of compressive force, and facilitates the supply of the raw material powder between the rolls and into the die, resulting in a molding effect. Is preferred because The lubricant may be an internal lubricant used after being mixed with the raw material powder before molding, or may be an external lubricant used by being applied to a die, a roll surface, or the like. . Examples of lubricants include, for example, water, lubricating oil, glycerin, silicon, graphite, talc,
Examples include magnesium stearate, molybdenum disulfide, ethylene glycol, paraffin and the like. In the tableting of the present invention, a nucleating agent may be used if necessary. The shape of the nucleating agent is not particularly limited, and examples thereof include a sphere, a lens, a column, and an irregular shape.

The compressor used in the present invention includes a tableting machine and a briquetting machine. Tableting machine used in the present invention is not particularly limited, for example, single-shot tableting machine, rotary tableting machine, one-point compression type machine, multi-point compression type machine,
Nucleated tablet presses, multilayer tablet presses, inclined roll type tablet presses, and the like. From the viewpoint of production, these include wet granule compression, dry granule compression, and direct powder compression. The operating conditions of the tableting in the present invention are not particularly limited, and vary depending on the used polyamino acid and other materials such as additives. The compressive force used in the tableting of the present invention is not particularly limited, but is generally 10 to 5000 kg / cm ² as the preload and 100 as the main pressure.
It is preferably from 0 to 50,000 kg / cm ² . The compression ratio of the tableting obtained by the present invention is not particularly limited, and varies depending on the use. Generally, the specific gravity of the obtained tablet is preferably 0.5 to 2.5.

The briquetting operation conditions in the present invention are not particularly limited, and vary depending on the polyamino acid used and other materials such as additives. For example, the roll rotation speed is generally preferably 5 to 20 rpm. In particular, if the material before compression has a lot of air or gas, increase the screw rotation speed of the feeder, slow down the rotation of the roll,
It is necessary to reduce the pocket volume. In general, the molding pressure is preferably from 1,000 to 10,000 kg / cm ² .
The temperature used is not particularly limited, but normal temperature is preferred.
However, depending on the material to be used, high-temperature briquetting, in which the material is heated to a high temperature and molded in a plasticized state, may be used. In use, when the air or gas contained in the material is large, the material may be deaerated and compressed. The compression molded article of the method can be dried if necessary. The drying temperature is not particularly limited, but in the case of ordinary drying, it is preferably 10C to 200C, and 40C to 120C.
Is particularly preferred. The obtained molded body may be further subjected to pulverization, crushing, sieving and the like.

(4-1-1) Method of Moistening the Molded Product Obtained by Compression Molding and Drying The molded product of the present invention is obtained by impregnating the molded product obtained by compression molding with moisture. And by a method of drying.
This method is one of the secondary moldings such as tabletting, briquetting, and compacting shown in (4-1). According to the method, when the method is applied, the compression molded body has a higher density. Here, when the amount of water used is reduced, the surface is modified, and when a sufficient amount of water is used, the entire surface is modified. The whole of which has been modified becomes a state close to a single gel when a sufficient amount of water is absorbed in the obtained molded body. In the method, the shape and size of the compression molded body used are as follows:
There is no particular limitation, and one having a shape and size according to the intended use may be used. As the shape, all shapes obtained by tabletting, briquetting, compacting and the like described in (4-1) can be used. The water used in the method may be water alone or may contain a binder, a salt and the like. The temperature is not particularly limited. The amount of water used in the method is reduced when only the surface of the target molded body is modified, and increased when the entire surface is modified.
In the case of surface modification, it is from 1 to 80% by weight, preferably from 5 to 50% by weight, based on the molding used. In the case of the overall modification, the amount is 80 to 1000% by weight, preferably 100 to 500% by weight, based on the molded body used.

The method of supplying water in this method is not particularly limited, and includes a method of spraying water, a method of applying water droplets, a method of dipping a compression-molded body in water, a method of contacting a medium containing water, and a method of humid water. And the like. The method for drying the water-compacted compact of the present invention is not particularly limited, and a commonly used drying method is used. At this time, if it is desired to maintain the shape of the compression molded body, a stationary type drying method is used, and the shape of the compression molded body is deformed. You can use it. The drying temperature is not particularly limited, but in the case of ordinary drying, it is preferably from 10 ° C to 200 ° C, and from 40 ° C to 1 ° C.
20 ° C. is particularly preferred. The obtained granules may be further subjected to pulverization, crushing, sieving and the like.

(4-2) Method of Forming Using Binder The molded article of the present invention is produced by a method of forming using a binder. The production method includes a method of forming a binder by using a binder and a solvent, and a method of forming a thermoplastic resin as a binder by melting the resin by heating and cooling the resin. Here, a method of forming a binder by using a binder and a solvent will be described. A method of using a thermoplastic resin as a binder, melting the resin by heating, and cooling the resin is described in (4-2). -1) will be described.

The method comprises dissolving or suspending a binder in a solvent, mixing and, if necessary, removing the solvent.
This is a method for obtaining a molded body. Among these, when the binder itself is a liquid, a solvent may not be required in some cases.
When a hydrophilic binder is used, water and / or a polar organic solvent is used as a solvent, and when a hydrophobic binder is used, a non-polar organic solvent is used.
The organic solvent of the present invention is not particularly limited, but a solvent which is easily removed and has high safety is preferable. For example, acetone, methanol, ethanol, isopropanol,
Examples include toluene, xylene, methylene chloride, chloroform, carbon tetrachloride and the like.

The binder used in the method is not particularly limited. For example, as the hydrophilic binder,
Starch, soluble starch, dextrin, pregelatinized starch, alginic acid, sodium alginate, gum arabic, tragacanth, locust bean gum, casein, sodium caseinate, gelatin, steam, and natural hydrophilic substances such as soy protein,
Hydrophilic semi-synthetic products such as sodium carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, sodium ligninsulfonate, calcium ligninsulfonate, sodium carboxymethylstarch, hydroxyethylstarch, sodium starch phosphate, hydroxypropylcellulose, hydroxypropylmethylcellulose, polyvinyl Alcohol, polyvinyl methyl ether, polyacrylamide, sodium polyacrylate, polyacrylamidopropyl sulfonic acid, polyethylene glycol, polyethylene oxide,
Hydrophilic synthetic products such as polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers and copolymers thereof, surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants Agents, sodium silicate, glycerin and the like. Further, as the hydrophobic binder, shellac, rosin, tall oil, animal and vegetable oils,
Hydrophobic natural products such as soybean oil, fish oil, beef oil, liquid paraffin, heavy oil, machine oil, spindle oil, etc., hydrophobic semi-synthetic products such as ethyl cellulose, acetyl cellulose, ester gum, polyvinyl acetate, cumarone resin, petroleum resin, phenol Examples include hydrophobic synthetic products such as resins.

It is also possible to use an adhesive obtained by improving the binder of the above method and improving the adhesiveness. Adhesives are classified into a solvent type and a reaction type which reacts during molding to cause crosslinking and the like. The granulation method used in the method is not particularly limited,
Extrusion molding is preferred. That is, a method in which a solvent is added to powder or granules of raw materials, mixed, and the mixture is extruded and granulated through a hole of a screen, a die or the like by an appropriate extrusion mechanism.

The machine used in the method is not particularly limited, and examples thereof include a pre-extrusion-type extrusion granulator, a lateral extrusion-type extrusion granulator, a vacuum extrusion-type extrusion granulator, and a pretreatment-type extrusion granulator. Roll extrusion granulators such as screw extrusion granulators such as granulators, cylindrical die horizontal extrusion granulators, cylindrical die vertical extrusion granulators, and disk die horizontal extrusion granulators. Blade-type extrusion granulators such as basket-type extrusion granulators, oscillating-type extrusion granulators, etc.
Drum type extrusion granulators such as a self-molding type extrusion granulator such as a gear type extrusion granulator and a cylinder type extrusion granulator, an intermittent type extrusion granulator and a continuous type extrusion granulator.

The particle size of the raw materials used in the method is not particularly limited and may be selected according to the purpose of use. However, a method in which the material can be easily passed through the holes of the die and the mixing is uniform is preferable. Generally, fine powder of 100 to 200 mesh or less is preferable. When the method is carried out in a dry manner, the raw materials preferably have fluidity. The raw material of the method preferably has plasticity exhibiting a thixotropy phenomenon, and if exhibiting a dilatancy phenomenon, it is preferable to add an excipient or a binder in some cases.

Examples of the binder include acetone, methanol, ethanol, gum arabic, sodium alginate, hydroxypropylcellulose, methylcellulose, sodium caseinate, glycerin, corn starch, sodium carboxymethylcellulose, gelatin, dextrin, starch, molasses, lactose, polyvinyl Examples include alcohol, polyvinylpyrrolidone, microcrystalline cellulose, pitch, sodium polyacrylate, polyethylene glycol, lignin, alumina sol, aqueous ammonia, sodium silicate, bentonite, and sodium polyphosphate. These act as thickeners, thinners, extenders, solvents, plasticizers, lubricants and the like.

The method of mixing the raw materials in the method is not particularly limited, but a mixer such as a kneader can be used.
In addition, the method of liquid addition is not particularly limited, and may be adjusted to the intended molded body. Although the post-treatment step of the method is not particularly limited, it is preferable to perform sizing. The method of sizing is not particularly limited, for example, a crushing sizing method,
A spherical sizing method may be used. The molded article of the method can be dried if necessary. The drying temperature is not particularly limited, but in the case of ordinary drying, it is preferably from 10 ° C to 200 ° C, particularly preferably from 40 ° C to 120 ° C. The obtained molded body may be further subjected to pulverization, crushing, sieving and the like.

(4-2-1) A method in which a thermoplastic resin is used as a binder, and the resin is melted by heating and then molded by cooling. The molded article of the present invention contains a thermoplastic resin as a binder. It can be manufactured by using a resin, melting the resin by heating and cooling. The thermoplastic resin used in the method is not particularly limited, and is a solid at room temperature, but softens and melts when heat is applied, and becomes solid again when returned to room temperature.
In addition to ordinary thermoplastic resin, it shows plasticity during molding,
Once heat is applied, crosslinking occurs between molecules due to heat, a crosslinking agent, and the like, and includes those that become cured after molding or during molding to become a thermosetting resin. In the present invention, both are referred to as a thermoplastic resin.

Examples of the thermoplastic resin used in the method include vinyl resins such as vinyl chloride resin, vinyl acetate resin and vinylidene chloride resin, high-density polyethylene, low-density polyethylene, polypropylene, acrylic resin, ABS resin, and polystyrene resin. , A styrene resin, a polyamide resin, an acetal resin, a polycarbonate resin, a polyester resin, and the like. Examples of the thermosetting resin after molding include a phenol resin, a urea resin, a melamine resin, an unsaturated polyester resin, an epoxy resin, and a polyurethane. Resins. Among them, when used for agricultural and horticultural purposes, it is preferable to have biodegradability because it is used in the environment and is difficult to recover. Examples thereof include aliphatic polyesters such as polylactic acid, polylactide, polybutylene succinate, polycaprolactone, polyhydroxybutyrate, polyhydroxyvalerate, and polyglycolic acid.

The amount of the thermoplastic resin used is as follows:
If the amount is too small, the effect as a binder is lost,
If the amount is too large, the sustained-release property and efficacy of the active ingredient decrease. In particular, since it has a significant effect on the sustained release of the active ingredient, the appropriate amount of the active ingredient cannot be generally specified, but is generally 5 to 90% by weight.
Is preferred, and 10 to 80% by weight is particularly preferred. In this method, a plasticizer, a stabilizer, a lubricant, a coloring agent, a reinforcing agent, an extender, and the like may be added as necessary, in addition to the polyamino acid and the thermoplastic resin.

The plasticizer is used to give softness to the molded article, and the stabilizer is used to prevent physical and chemical deterioration during molding or during storage of the molded article. The lubricant is added to improve fluidity and processability at the time of molding, or to facilitate extraction from a mold. The reinforcing agent is for improving the strength and durability of the molded article, and the extender is for limiting the amount of the active ingredient in the molded article or reducing the price of the molded article. In this method, the steps are not particularly limited, but generally comprise mixing, kneading, granulating, and dehydrating and drying steps.

The apparatus used for mixing includes a mixer such as a ribbon blender, a Henschel blender, and a drum blender. Examples of the kneading include a mixing roll, an intensive mixer, a short-screw extruder, a high-speed twin-screw continuous mixer, and the like. Examples of the apparatus used for granulation include a granulator for a cold cut method such as a sheet cut method and a strand cut method, and a granulator for a hot cut method such as an air hot cut method and an underwater cut method. The dehydration and drying step is necessary when granulation is performed by an air hot cut method or an underwater cut method, and examples thereof include a centrifugal dryer. The kneading temperature in this method depends on the resin used, and an appropriate temperature may be appropriately selected.

(5) Water retention and sustained release of the molded product containing the polyamino acid The effects of the molded article of the present invention are water retention and sustained release of the drug.
The required water retention and sustained release characteristics differ depending on the intended use and purpose. Water retention is required for a certain period of time, and in some cases, it is preferable that the water retention disappears after a certain period of time. If the water retention is not sufficient, the water retention effect is thin, and in the case of a water-absorbent resin having too high a water retention represented by a crosslinked polyacrylic resin, root rot is likely to occur, and the water content under drying is low. When it is low, the water in the gel cannot be used effectively by the plants. Gels of polyamino acids
The plant can effectively utilize the water in the gel even under dry conditions without causing root rot of the plant. As for the amount of polyamino acid in the molded body, the larger the amount used, the higher the water retention,
If the amount is small, the water retention is low, but the appropriate amount of use can not be said unconditionally because there is a balance with the sustained release of the drug,
It is preferably from 1 to 80% by weight, more preferably from 10 to 50% by weight, based on the weight of the whole molded body. However, when emphasis is placed on water retention, 50 to 100% by weight is preferable,
60-100% by weight is more preferred. With respect to sustained release, the molded article of the present invention works effectively when it is desired to maintain the effect over a long period of time, when it is desired to exhibit the effect efficiently in a short period of time, or when it is desired to maintain a certain amount of effect for a certain period of time. This is effective when an effect is desired to appear after a certain period of time.

The method for controlling the sustained release of a molded article of the present invention is a method of controlling the disintegration of a molded article and the sustained release of a polyamino acid gel with a drug. Specific factors include the type or content of the polyamino acid, the active ingredient, the molding method, the strength and disintegration of the molded product, the type of the additive, and the content thereof.

The sustained-release property of the polyamino acid gel is related to the entire region from the early stage to the late stage of the release of the drug (active ingredient). The effect of the polyamino acid on sustained release depends on the affinity between the polyamino acid and the active ingredient and the degree of gelation of the polyamino acid. Since polyamino acids have high hydrophilicity, active ingredients with high hydrophilicity have high affinity with polyamino acid gels and are difficult to release, whereas active ingredients with high hydrophobicity have low affinity and are easily released. . As the swelling rate of the polyamino acid gel increases, the release of the drug becomes easier.

The disintegratability of the molded product is related to a range from the early stage to the middle stage of the release of the drug (active ingredient). When the content of the polyamino acid is increased, the disintegration of the molded article is promoted, so that the initial release rate is increased. On the other hand, when the amount of the polyamino acid is small, the disintegration is controlled by other components. As for the effect on the sustained release of the active ingredient, generally, those having high hydrophilicity have a short period of sustained release, and those having high hydrophobicity or low solubility in water have a long period of sustained release. . The difference in sustained release due to the molding method is strongly influenced by other factors and cannot be stated unconditionally, but as a general trend, the sustained release of compression molded articles is performed in a short period of time. The re-treated one has a longer sustained release period. Those manufactured by extrusion granulation or the like using a binder have a sustained release property shorter than that of a compression molded product. On the other hand, those that are melted using a resin have a longer sustained release property.
Among these factors, the molding method and the content of the polyamino acid particularly affect the sustained release.

(6) Use of the molded product containing polyamino acid The use of the polyamino acid molded product of the present invention is not particularly limited, and water absorption of agricultural and horticultural products, pharmaceutical products, food products, bath additives, sanitary materials, etc. It can be used for applications in which conductive resins can be used. Among them, the one that works most effectively for water retention and chemical sustained release is for agricultural and horticultural applications. Hereinafter, the case of using for agricultural and horticultural purposes will be described in detail.

(7) Composition of Soil Composition Containing Polyamino Acid Compressed Molded Article The molded article of the present invention can be mixed with soil and used as a soil composition. Examples of the soil used in the soil composition of the present invention include, for example, hard akadama soil, baked akadama soil, hard kanuma soil, mulch, black soil, Kiryu sand, pumice sand, Fuji sand, Yahagi sand, Arakida sand, river sand, morning sand , Keto earth, vermiculite, charcoal, humid earth, clay and the like. Alternatively, soils such as fields and sands to which the soil composition is applied or other soils can be used. These may be used alone or in combination as a culture soil. At this time, the composition can be adjusted according to the type of plant or the form to be used. If desired, peat moss may be added.

The soil used in preparing the soil composition is as follows:
When the soil composition is prepared, it is not particularly limited as long as it can exhibit substantially sufficient water retention and ventilation effects at the same time, and its form may be powder or granular. Generally, a particle size of about 5 to 50 mesh (dry state) or a particle size of about 0.5 to 5.0 mm (dry state) capable of expressing coarse pores with excellent air permeability and water permeability. Granulated ones are preferred. If necessary, the soil composition may contain various useful components other than those contained in the molded body.
For example, moisture, organic fertilizer, biological fertilizer, chemical fertilizer, compost,
Chicken dung, organic materials, pH adjusters, surfactants, foaming agents,
Corrosive substances, water retention and fertility-improving mineral substance powders (bentonite, zeolite powder, etc.), pesticides (pesticides, fungicides, herbicides, fungicides, etc.), plant vitalizers, plant life prolonging agents, insect pests and animals Repellent, soil penetrant, trace element nutrient, diatomaceous earth, clay, lime, phytohormone, mineral, coral sand, activated carbon, calcium carbonate, magnesium carbonate, kaolin, clay, alumina, silica, titanium oxide, talc, diatomaceous earth , Mica, shirasu balloon, inorganic particles such as glass beads, synthetic resin pellets, beads, coarse particles, wood chips, sawdust, cereal flour, crushed plant shells and stems, plant seeds, fungi, ferguson Micro-radioactive minerals such as
Examples include far-infrared radiation ceramics, ethylene gas-absorbing minerals such as Otani stone and zeolite, inorganic water retention materials such as pearlite, pumice, and vermiculite, and water-absorbing resins other than crosslinked polyamino acid-based resins.

It is preferable that these additives have biodegradability from the viewpoint of environmental protection. In many of these additives, the components in the molded body exhibit a sustained release property, whereas the additives in the molded article exhibit a rapid effect. In addition, when it is desired to further improve the water retention of the soil composition of the present invention, a powdery or granular polyamino acid may be added. Further, if necessary, another water absorbing resin may be contained. Further, the soil composition of the present invention may be made into a solid substance by a binder. Examples of binders include fully fermented oil scum, clay, acrylate latex, styrene butadiene latex, vinyl acetate latex, acrylic acid-acrylamide propane sulfonamide-copolymer, partially saponified polyvinyl alcohol, and the like. Can be
These binders preferably have biodegradability from the viewpoint of environmental protection.

(8) Method and place of use of molded article containing polyamino acid The method of use and place of use of molded article containing polyamino acid are not particularly limited, but the molded article or soil composition is sprayed on the fields as topsoil. There is a method used as a culture soil for nursery beds and the like. Also, it may be applied to paddy fields, rivers, ponds, moats, the sea, etc. Spraying may be performed manually or using a machine. There is also a method of spraying from the air using a helicopter, an airplane, a radio control airplane, or the like. In addition, a method of burying a predetermined amount of the molded body containing the polyamino acid in the soil as particles, or as a gel swollen with water, liquid fertilizer, or the like,
The method of spraying or filling the fields solidified with the binder in the fields may be used. Also. It may be contained in a molded seedling or the like and transplanted together with the plant. Alternatively, a method of mixing while plowing the soil may be used. The form of the plant to be used can be used in a wide range, and is not particularly limited as long as the plant is cultivated. For example, seed germination, seedling raising, leaf vegetables, fruit vegetables, root vegetables, flower growing, etc., planting of adult trees Can be used for replacement.

[0069]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples. In the following Examples and Comparative Examples, “parts” means “parts by weight”. (1) Measurement of biodegradability Biodegradability was measured by a compost method. The composting method is an application of ASTM D-5338.92, an ISO
Performed according to CD 14855. That is, first, the amount of carbon contained in the test sample was measured by elemental analysis.
Next, 15 parts of the test sample was added to 800 parts of the inocula, and the test was carried out at 58 ° C. for 40 days, the amount of carbon dioxide generated was measured, and the amount of carbon contained in the test sample was calculated based on the amount converted to carbon dioxide. The amount of generated carbon dioxide was expressed as a biodegradation rate (%). Here, some of the samples that are easily biodegradable promote the decomposition of even the carbon content in the inocula, and in this case, some of the samples have a value exceeding 100%.

(2) Tea Bag Method The amount of water absorption was measured for tap water. That is,
Approximately 0.03 parts of the water-absorbent resin is used for a non-woven tea bag (8
0 mm x 50 mm) and immersed in an excess solution to swell the resin for 1 hour.
Drained for minutes and weighed. Assuming that the same operation was performed using only the tea bag as a blank, the value obtained by subtracting the weight of the blank and the weight of the water-absorbent resin from the measured value was divided by the weight of the water-absorbent resin, and the amount of water absorption (g / g of resin) ).

(3) Plant Growth Test Plant growth tests were carried out using a cucumber seedling growth test and a geranium seedling transplantation growth test. In addition,
The result of the cucumber seedling raising test was determined by observing the degree of leaf withering or the growth index 25 days after the growth.
The growth index was calculated as follows. That is, the grown plants are taken out together with the roots, washed with water to remove mud and the like, and the excess water is absorbed with a paper towel, and divided into above and below parts or between leaves and root parts.
/ Book) was measured. Next, it air-dried and the air-dry weight (g / book) per one was calculated. The obtained fresh weight and air-dried weight were expressed as a percentage (%) with respect to the fresh weight and air-dried weight of the plants in the standard section grown under the same growth conditions except that the molded body was included, except that the weight was 100. In addition, a growth test using geranium seedlings was performed by transplanting geranium seedlings using soil contaminated with seedling blight, performing a growth test for 60 days, and calculating the control rate of seedling blight. . In this control group, a 1000-fold diluted solution of Tatigalen wettable powder (manufactured by Sankyo) was added.
50 ml per plant was used.

Compound Production Example 7.2 parts of lysine methyl ester dihydrochloride and lysine 1
22.6 parts of the hydrochloride was dissolved in 40 parts of distilled water, and 7.8 parts of caustic soda was added little by little to neutralize the solution, thereby preparing an aqueous lysine solution. On the other hand, under nitrogen stream, 100 parts of polysuccinimide having a molecular weight of 96,000 was dissolved in 400 parts of DMF, an aqueous solution of lysine was added, and the mixture was stirred at room temperature for 1 hour.
Reacted for hours. The reaction product was transferred to a mixer equipped with a blade with stirring blades, 400 parts of distilled water and 400 parts of methanol were added, and the gel was shredded at 8000 rpm for 5 minutes.
129.7 parts of a 7% by weight aqueous sodium hydroxide solution was added dropwise over 2 hours. After the dropwise addition, the mixture was further stirred for 2 hours, and neutralized with 7% by weight aqueous hydrochloric acid until pH = 7. After neutralization, 300 parts of methanol was further added, and the precipitate was dried at 60 ° C.
Further, the mixture is pulverized using a sample mill to obtain a water-absorbing polymer 1
43 parts were obtained. When the biodegradability of this resin was examined, the biodegradability was as good as 102%, and the water absorption with tap water was 290 times.

Comparative Example of Compound Production A crosslinked polyacrylic acid was produced according to the method of JP-B-54-30710. Although the water absorption of this resin with respect to tap water was as good as 270 times, when the biodegradability was examined, the biodegradation rate was 2.2%, showing no biodegradability.

Molded product production example 1 The crosslinked polyaspartic acid obtained in the compound production example 0.1.
42 parts were put into a tableting machine (Model 7A-SM manufactured by Kikusui Seisakusho) with a die of 10 mm in diameter, and the upper punch was adjusted so that the thickness of the tablet was 4 mm, and the tablet was pressed. Tablets were obtained.

Molded product production example 2 The crosslinked polyaspartic acid 10 obtained in the compound production example
When 00 parts were granulated using a briquetting machine (trade name K-205, manufactured by Otsuka Iron Works Co., Ltd.), a sheet-like molded product was obtained. This sheet-like molded body was crushed using a hammer mill, and amorphous granules were obtained.

Molded Article Production Example 3 One part of distilled water was sprayed on the tablet obtained in Molded Article Production Example 1,
It was dried in a dryer at 60 ° C. to obtain tablets.

Molded product production example 4 Crosslinked polyaspartic acid 20 obtained in compound production example 20
Part, talc 75 parts, advanced 16 chemicals (Mitsui Toatsu Fertilizer Co., Ltd.)
5 parts) was placed in a mixer and mixed until uniform.
0.42 parts of the obtained mixture was put into a tableting machine (Model 7A-SM manufactured by Kikusui Seisakusho) with a die having a diameter of 10 mm, and the upper punch was adjusted so that the thickness of the tablets was 4 mm. Then, a disc-shaped tablet was obtained at the corner.

Molded product production example 5 Crosslinked polyaspartic acid 20 obtained in compound production example
, 78 parts of bentonite and 2 parts of Tachigaren wettable powder (manufactured by Sankyo Co., Ltd.), 25 parts of water were added, mixed using a tabletop kneader, extruded from a screen having a diameter of 4 mm, and further dried at 60 ° C. for 6 hours. Then, a pellet was obtained.

Molded Article Production Example 6 The crosslinked polyaspartic acid 80 obtained in the compound production example 80
Part and powdered polylactic acid (trade name LA, manufactured by Mitsui Chemicals, Inc.)
CEA) 116 parts, Tachigaren wettable powder 4 parts, Labo Plastomill 80C100 (manufactured by Toyo Seiki Co., Ltd.) with resin temperature 18
After mixing at 0 to 190 ° C. and extruding from a 4 mm diameter screen, pellets were obtained.

Molded Article Production Example 7 4 parts of the crosslinked polyaspartic acid obtained in the compound production example, 0.2 part of tatigalen wettable powder, 10% by weight of polylactic acid (LACEA, manufactured by Mitsui Chemicals, Inc.) -Mix 58 parts of chloroform solution while diffusing vigorously,
mm cylindrical mold at room temperature, 100mmgHg
The chloroform was distilled off for 1 hour and further dried at 60 ° C. for 4 hours to obtain a pellet.

Molded Article Production Example 8 The crosslinked polyaspartic acid 80 obtained in the compound production example 80
, 4 parts of Tatigaren wettable powder and 20 parts of starch paste were mixed using a tabletop kneader, extruded from a screen having a diameter of 4 mm, and dried at 60 ° C for 6 hours to obtain pellets.

Comparative Example 1 for Production of Molded Product The same procedure as in Example 1 for producing a molded product was carried out except that the crosslinked polyacrylic acid obtained in Comparative Example for Production of Compound was used instead of the crosslinked polyaspartic acid of Production Example 1 for tablets. was gotten.

Comparative Example 2 for Production of Molded Product A tablet was obtained by using 95 parts of talc and 5 parts of advanced 16 chemical conversion in the same manner as in Production Example 1 of molded product, without using the crosslinked polyaspartic acid of Production Example 4.

Molded article production comparative example 3 Instead of the crosslinked polyaspartic acid of molded article production example 4,
Using the crosslinked polyacrylic acid obtained in the compound production comparative example, a tablet was obtained in the same manner as in molded article production example 1.

Molded article production comparative example 4 Instead of the crosslinked polyaspartic acid of molded article production example 6,
Pellets were obtained by using the crosslinked polyacrylic acid obtained in the compound production comparative example in the same manner as in molded article production example 6.

Example 1 170 parts of Super Soil No. 2 (horticultural floor soil) were placed in a 500 ml plastic pot as a cultivation soil, and the three molded products obtained in the molded product production example 1 were placed.
Zero parts were laid on it. Using this soil composition, a growth test was carried out using cucumber as a test crop. For irrigation, sufficient irrigation was first performed until saturation, and then a growth test was performed for 10 days without irrigation. The test was further performed until the 25th, and the dry weight of leaves, roots and above-ground parts was measured. The cucumber was transplanted to a pot at the time of cotyledon (futaba) development 5 to 7 days after seeding. The number of repetitions was 10, and the average of 10 times was calculated. As a standard plot, water was added up to 10 days after transplantation without adding a water retention agent.
The part was irrigated four times, and thereafter, was subjected to sufficient standard irrigation every day until 25 days. As a result, after 25 days, the main stem length was 13.8 cm, the stem dry weight was 0.33 parts / row, the growth index was 141, the leaf dry weight was 0.87 parts / row, and the growth index was 15
8. The dry weight of the root is 0.1454 parts / tree and the growth index is 18.
0, the dry weight of foliage was 1.19 parts / row, and the growth index was 152, indicating remarkable growth promotion.

Example 2 0.4 parts of the granules obtained in Production Example 2 of a compact were thoroughly mixed with 200 parts of Super Soil No. 2 (horticultural floor soil), and the obtained soil composition was used in Example 1 A plant growth test was performed using cucumber in the same manner as described above, with the number of times of irrigation restricted. As a result, after 25 days, the main stem length was 14.0 cm and the stem dry weight was 0.
The growth index is 148 at 34 parts / tree, the leaf dry weight is 0.88 parts / row, the growth index is 160, and the root dry weight is 0.1486 parts / tree.
In this book, the growth index was 184, the foliage dry weight was 1.18 parts / book, and the growth index was 151, indicating remarkable growth promotion.

Example 3 In the same manner as in Example 1, the molded article 3 obtained in the molded article production example 3
A plant growth test was carried out using cucumber in the same manner as in Example 1 while limiting the number of times of watering. As a result, 25 days later, the main stem length was 13.6 cm, the stem dry weight was 0.32 parts / tree, the growth index was 139, the leaf dry weight was 0.86 parts / tree, the growth index was 156, and the root dry weight was 156. The growth index was 179 at 0.1446 parts / row, and the foliage dry weight was 1.15 parts / row, and the growth index was 147, indicating remarkable growth promotion.

Example 4 Using the molded product obtained in molded product production example 4, using Super Soil No. 2 (horticultural floor soil) as a cultivation soil, adding a resin to a concentration of 0.1% by weight. And mixed well to form a soil composition. A plant growth test was performed on this soil composition for 25 days using cucumber as a test crop at a standard watering rate of 26.3 ml / day. The measurement was performed on the air-dried weight of the above-ground part and the underground part, and the growth index was calculated. The number of repetitions was 10, and the average of 10 times was calculated. In addition, as a standard plot, do not add a water retention agent,
A solution obtained by diluting the advanced 16 chemical fertilizer with water 20 times was irrigated with 50 ml per strain, and then grown using standard irrigation. As a result, the above-ground growth index was 172,
Underground growth index was 196, indicating remarkable growth promotion.

Example 5 Soil contaminated with seedling damping was collected, geranium seedlings were transplanted, and the molded product obtained in molded product production example 5 was pierced with a hole having a depth of 3 to 5 cm around the plant. Opening and feeding were performed, and a growth test was performed for 60 days in standard irrigation. The number of repetitions was 20, and the result of integrating the 20 times was shown. As a result, the control rate of seedling damping off was almost 100%, and no chemical damage or root rot was observed.

Example 6 A growth test of geranium was performed in the same manner as in Example 5 using the molded body obtained in Production Example 6 of the molded body. As a result, the control rate of seedling damping off was almost 100%, and no chemical damage or root rot was observed.

Example 7 A geranium growth test was carried out in the same manner as in Example 5 using the molded article obtained in the molded article production example 7. As a result, the control rate of seedling damping off was almost 100%, and no chemical damage or root rot was observed.

Comparative Example 1 A cucumber was prepared in the same manner as in Example 1 except that the molded article made of crosslinked polyacrylic acid obtained in Comparative Example 1 was used instead of the molded article of Example 1. Was subjected to a growth test under the restriction of the number of times of watering. As a result, after 25 days, the main stem length was 12.7 cm, the stem dry weight was 0.17 parts / tree, the growth index was 80, the leaf dry weight was 0.47 parts / tree, the growth index was 85, and the root dry weight was 85%. The growth index is 91 at 0.074 parts / book,
The dry weight of foliage was 0.71 parts / row and the growth index was 91, indicating growth inhibition.

Comparative Example 2 In Example 4, the same procedure as in Example 1 was carried out except that the molded article obtained in Comparative Example 2 was used instead of the molded article in Example 4, except that the cucumber was subjected to standard irrigation. A growth test was performed.
As a result, the above-ground growth index was 122 and the underground growth index was 115, but root rot was observed at 20%.

Comparative Example 3 In Example 4, the same procedure as in Example 4 was repeated except that the molded article obtained in Comparative Example 3 was used instead of the molded article of Example 4, and the cucumber was subjected to standard irrigation. A growth test was performed.
As a result, the above-ground growth index was 114 and the underground growth index was 109, indicating little promotion of growth.

Comparative Example 4 Production of Molded Article The geranium growth test was carried out in the same manner as in Example 5 using the molded article obtained in Comparative Example 4. As a result, root rot was observed in 30% of the seedlings 10 days after transplantation.

[0097]

According to the present invention, it is possible to provide a molded article which does not accumulate in soil after use, has excellent water retention, and promotes the growth of plants.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 67/04 C08L 67/04 79/08 79/08 (72) Inventor Hiroaki Tamaya 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals (72) Inventor Chiaki Morooka 2000 Togo, Mobara-shi, Chiba Mitsui Chemicals Co., Ltd.

Claims (25)

[Claims] 1. A molded article containing a polyamino acid. 2. In addition to the polyamino acid, a binding agent,
And / or a molded article comprising a resin composition containing a biologically active component. 3. The molded article according to claim 2, wherein the binder contains a binder resin and / or a clay. 4. The molded article according to claim 3, wherein the binder resin is a biodegradable resin. 5. The molded article according to claim 4, wherein the biodegradable resin is an aliphatic polyester. 6. The molded article according to claim 5, wherein the aliphatic polyester is polylactic acid. 7. The molded article according to claim 2, wherein the binder contains an adhesive. 8. The molded article according to claim 1, wherein the biologically active component contains a pesticide. 9. The molded article according to claim 1, wherein the bioactive component contains a fertilizer. 10. The molded article according to claim 1, wherein the polyamino acid is partially crosslinked. 11. The molded article according to claim 1, wherein the polyamino acid is an acidic polyamino acid. 12. The molded article according to claim 1, wherein the polyamino acid is polyaspartic acid. 13. The molded article according to claim 1, wherein the molded article is a granular shaped article. 14. The molded article according to claim 1, wherein the molded article is a tablet-shaped molded article. 15. The molded article according to claim 1, wherein the molded article is a sheet-shaped molded article. 16. The method for producing a molded article according to claim 1, wherein compression molding is performed. 17. The method for producing a molded article according to claim 1, wherein tabletting is performed. 18. The method for producing a molded article according to claim 1, wherein briquetting is performed. 19. The method for producing a molded article according to claim 1, wherein briquetting is performed. 20. The method for producing a molded article according to claim 1, wherein the molded article obtained by compression molding is impregnated with moisture and further dried. 21. The method for producing a molded article according to claim 1, wherein a binder and a polyamino acid are mixed and molded. 22. The method according to claim 1, wherein a thermoplastic resin is used as the binder resin and the binder resin is heated and melted.
The method for producing a molded article according to any one of the above. 23. The method according to claim 1, wherein the solution of the binder resin and the polyamino acid are mixed, and the solvent is removed.
16. The method for producing a molded article according to any one of items 15 to 15. 24. A soil composition containing the molded article according to claim 1. 25. A soil improvement method, comprising applying the molded article according to claim 1 to soil.