JP2000198858A - Crosslinked polyamino acid-containing particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide crosslinked polyamino acid-containing particles excellent in points of a water absorbing speed, biodegradability, a stickiness inhibiting property, a water retention characteristic and a sustain-release property, and useful for hygienic materials and soil conditioners. SOLUTION: This crosslinked polyamino acid-containing particle has a core/ shell structure, wherein the core phase comprises the crosslinked polyamino acid-containing particle and the shell phase comprises a coating material or a resin. The method for producing the particle comprises a step in which the surface of the crosslinked polyamino acid particle is coated with the coating material dissolved in a solution or existing in a molten state, or the resin dissolved in a solution or existing in a molten state to form the shell phase.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to biodegradable crosslinked polyamino acid-containing particles whose surface is coated with a coating material or a resin, and a method for producing the same. More specifically, the present invention relates to crosslinked polyamino acid-containing particles which have excellent water absorption, have a high water absorption rate, are less sticky at the time of use, are capable of sustained release of an active ingredient, and are easily decomposed at the time of disposal.

[0002]

2. Description of the Related Art [Technical background of water-absorbent resin] A water-absorbent resin is a resin that can absorb water of several tens to several thousand times its own weight. For example, an acrylic water-absorbent resin is known.
These water-absorbing resins are widely used in disposable hygiene articles because of their high water-absorbing properties. However, conventional water-absorbing resins have no decomposability, and there is a problem in a method for treating sanitary articles containing the same. Therefore, there has been a strong demand for a water-absorbing resin having a high water absorption rate and having biodegradability.

[Water-retaining material using water-absorbing resin] On the other hand, a highly water-absorbing resin that absorbs water several hundred times its own weight is mixed with soil to improve the water retention of the soil and to gradually release the active ingredient. It is well known that it is expected to play an important role in environmental protection such as desert greening and desertification prevention. However, if the water retention material is not biodegradable, it will accumulate in the ground during long-term use, which may cause problems.

[Technical background of cross-linked polyamino acid resin]
It has been shown that polyamino acids are absorbed and digested by enzymatic action even when absorbed into the body, do not show antigenicity in the body, and have low inflammatory properties to the skin and mucous membranes of the organism. Therefore, it is a material that is kind to people. These have been studied as biopolymer models for a long time, and research on their use for artificial leather, drug carriers, cosmetics, and the like has been conducted. As an example of such a resin,
Polyaspartic acid, poly-γ-glutamic acid, and polylysine have been found in nature.

[0005] 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 is 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-growing soil composition used in a seedling-growing pot (Japanese Patent Application Laid-Open No. 8-337775). This composition is a composition containing cross-linked polyaspartic acid, and is useful because it promotes plant root survival. The resin obtained by crosslinking these polyamino acids has the property that it absorbs water and swells, and the water once absorbed is hard to release even when a load is applied. Since it has water retention and biodegradability,
Polyamino acids are environmentally friendly materials. As a method for producing these crosslinked polyamino acids, for example, a method of crosslinking an acidic amino acid to obtain a hydrogel (Akam
atsu et al., U.S. Patent No. 3,948,863;
No. 41309, Iwatsuki et al., JP-A-5-279416.
No. 6), polyaspartic acid, a method of reacting aspartic acid with a cross-linking agent by heat (Sikes et al., JP-A-6-5062).
No. 44; U.S. Pat. Nos. 5,247,068 and 52,849.
No. 36, Suzuki et al., JP-A-7-309943, Harada et al.
JP-A-8-59820), a method of irradiating poly-γ-glutamic acid with γ-rays (Kunioka et al., Journal of Polymers, Vol. 50, No. 1)
0, p. 755 (1993)).

The present inventors have also disclosed in Japanese Patent Application Laid-Open No. 7-2241.
No. 63 disclosed a method of crosslinking a polysuccinimide with a diamine and hydrolyzing the remaining imide ring with an alkali to obtain a water-absorbing resin having a high saltwater-absorbing ability.

[0007]

The water-absorbent resin used for sanitary goods is a large amount of bodily fluids such as urine, blood, menstrual blood and sweat.
And it is required to be absorbed promptly. Its water absorption rate is affected by its surface area. When the total weight of the water-absorbing resin particles used is constant, the larger the particles, the smaller the sum of the surface areas, and the smaller the area in contact with water, the lower the water absorption speed. Conversely, the finer the particles, the greater the sum of the surface areas and the faster the water absorption rate.

However, even if the particles of the water absorbent resin are fine,
When it comes into contact with water, so-called "mamako" is generated, which may not increase the water absorption rate. When the water-absorbent resin comes into contact with water, only the surface of the water-absorbent resin absorbs water, and the surface becomes sticky, preventing water from penetrating into the interior of the particle aggregate. It is considered a state.

In addition, when performing operations such as mixing or spraying a water-absorbent resin with soil, if the humidity is high, the resin absorbs moisture in the air and the surface becomes sticky, so that agricultural tools,
It easily adheres to shoes and the like. In addition, when mixing with soil, the gel easily absorbs water in the soil and hardens, making uniform mixing difficult. Furthermore, when a useful component is given to a plant, the water-absorbent resin releases the useful component in a short time, so that a sustained release property that maintains the effect of the active component for a long time cannot be expected.

[0010] An object of the present invention is to solve the above-mentioned problems of the prior art, and has a high water absorption rate, has biodegradability, has no stickiness due to moisture absorption or soil moisture, and has a sustained release property of an active ingredient. And to provide a crosslinked polyamino acid-containing particle having excellent water retention ability and a method for producing the same.

[0011]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that by coating the surface of a biodegradable crosslinked polyamino acid with a coating material or a resin, the Mamako phenomenon can be prevented. The present invention has been found to be able to prevent the occurrence of water absorption, to prevent stickiness, to exhibit a sustained release property and a water retention effect, and to complete the present invention.

That is, the present invention has a core / shell structure in which at least a part of the surface of a core phase is covered with at least one shell phase, and the core phase is constituted by at least particles containing cross-linked polyamino acid. Are crosslinked polyamino acid-containing particles which are constituted by containing a coating material and / or a resin.

Further, the present invention relates to a method for producing the crosslinked polyamino acid-containing particles, wherein the surface of the crosslinked polyamino acid-containing particles is a coating material solution or a molten coating material, or a resin solution or a molten solution. A method for producing crosslinked polyamino acid-containing particles, comprising a step of forming at least one shell phase on at least a part of the surface by applying a resin.

Further, the present invention is a sanitary material and a soil conditioner containing the crosslinked polyamino acid-containing particles.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below.

(1) Structure of Crosslinked Polyamino Acid The particles of the present invention are produced using a crosslinked polyamino acid. This crosslinked polyamino acid has a structure in which a part of the polyamino acid is crosslinked. The basic skeleton of the crosslinked polyamino acid used in the present invention comprises a polypeptide obtained by dehydration condensation of an amino acid or an amino acid derivative. Specific examples of amino acids include 20 types of amino acids classified into the following four types. . Amino acids with non-polar, ie hydrophobic, R groups:
Alanine, valine, leucine, isoleucine, methionine, tryptophan, phenylalanine, proline. . Polar but uncharged amino acids: glycine, serine, threonine, cysteine, tyrosine, asparagine, glutamine. . Amino acids having a positively charged R group: lysine, histidine, arginine. . Amino acids having a negatively charged R group: aspartic acid, glutamic acid.

Other specific examples include L-ornithine, a series of α-amino acids, β-alanine, γ-aminobutyric acid, neutral amino acids, acidic amino acids, ω-esters of acidic amino acids, basic amino acids, basic amino acids And amino acid derivatives such as aspartic acid-L-phenylalanine dimer (aspartame) and aminosulfonic acids such as L-cysteic acid. α
-Even when the amino acid is in an optically active form (L-form, D-form),
It may be racemic.

The polyamino acid may be a copolymer containing other monomer components. Specific examples of the monomer component of the copolymer include aminocarboxylic acid, aminosulfonic acid,
Examples include aminophosphonic acid, hydroxycarboxylic acid, mercaptocarboxylic acid, mercaptosulfonic acid, and mercaptophosphonic acid. Further, polyamines, polyalcohols, polythiols, polycarboxylic acids, polysulfonic acids, polyphosphonic acids, polyhydrazine compounds, polycarbamoyl compounds, polysulfonamide compounds, polyphosphonamide compounds , Polyvalent epoxy compounds, polyvalent isocyanate compounds, polyvalent isothiocyanate compounds, polyvalent aziridine compounds, polyvalent carbamate compounds, polyvalent carbamic acid compounds, polyvalent oxazoline compounds, polyvalent reactive unsaturated bond compounds, Valent metals and the like can also be mentioned. When it is a copolymer, it may be a block copolymer or a random copolymer. Further, a graft structure may be used.

Among these, it is preferable to use polyaspartic acid, polyglutamic acid and polylysine, which are homopolymers having excellent biodegradability, as the basic skeleton. Further, polyaspartic acid having high water absorption, more preferably a polyglutamic acid as the basic skeleton, particularly,
Polyaspartic acid suitable for industrial production is most preferred.

The side chain structure of the cross-linked polyamino acid used in the present invention may be a polyamino acid residue having no substituent or a structure obtained by introducing another substituent into the polyamino acid residue. . For example, polyaspartic acid has a carboxyl group because it has a structure in which an imide ring is simply opened, but another substituent may be introduced as a pendant group into this structure. Examples of the other substituent include an amino acid residue such as lysine, a hydrocarbon group having a carboxyl group, and a hydrocarbon group having a sulfonic acid group.

In addition, the carboxyl group or side chain group of the acidic polyamino acid is attached to an amide bond of the polymer main chain.
It may be connected to any position. For example, in the case of an aspartic acid residue, it may be substituted at the α-position or at the β-position. For glutamic acid residues, α
It may be substituted at the γ-position or at the γ-position. The binding portion between the basic skeleton of the acidic polyamino acid and the side chain is not particularly limited. For example, an amide bond, an ester bond, a thioester bond and the like can be mentioned.

The carboxyl group of the crosslinked polyamino acid may be in a form in which a hydrogen atom is bonded or in a form in which a salt is formed. Examples of the counter ion of the carboxyl group include alkali metal salts, ammonium salts, and amine salts.

The polyamino acid in the particles of the present invention is a crosslinked product. The crosslinked portion and side chain portion of the crosslinked polyamino acid 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, an optionally substituted naphthyl group, a carbon atom An optionally branched alkoxy group having 1 to 18 atoms, an aralkyloxy group, a phenylthio group, an optionally branched alkylthio group having 1 to 18 carbon atoms, or an optionally branched alkylthio group having 1 to 18 carbon atoms Alkylamino group, optionally branched dialkylamino group having 1 to 18 carbon atoms, 1 to 18 carbon atoms
A trialkylammonium group, a hydroxyl group, an amino group, a mercapto group, a sulfonyl group, a sulfonic acid group, a phosphonic acid group which may be branched and salts thereof, an alkoxycarbonyl group, an alkylcarbonyloxy group and the like.

(2) Method for producing crosslinked polyamino acid The method for producing the crosslinked polyamino acid used in the present invention is not particularly limited. For example, Japanese Patent Application Laid-Open No. 7-224163, Vol. 50, No. 10, 755 (1993), U.S. Pat.
No. 863 (Japanese Patent Publication No. 52-41309), Japanese Patent Laid-Open No. 5-2
No. 79416, JP-A-6-506244 (U.S. Pat. Nos. 5,247,068 and 5,284,936);
No. 309943 can be used.

In addition, crosslinking by crosslinking of polyglutamic acid with a crosslinking agent, crosslinking of polylysine with a crosslinking agent, gamma-ray crosslinking of polyaspartic acid, gamma-ray crosslinking of polylysine, crosslinking of polyaspartic acid, polyglutamic acid, polylysine by electron beam, etc. Polyamino acids can be produced.

(3) Structure and Size of Crosslinked Polyamino Acid-Containing Particles The crosslinked polyamino acid-containing particles of the present invention comprise an internal core phase and a shell phase containing a coating material and / or a resin. It has a core / shell structure.

[Concept of the word "particle"] The term "particle" as used herein completely encompasses the concept that these words generally have in polymer chemistry, but is not necessarily equivalent. Absent. The morphology of the “particles” used in the present specification as observed by a scanning electron microscope is not limited to a spherical morphology, but also includes, for example, raspberry-like or gold rice sugar (confinit, Portuguese
o) An aspect having many projections, an erythrocyte flat aspect, a rugby ball-like spheroid-like aspect, an Escherichia coli-like spindle-like aspect, a thunder squirrel (a famous confectionery of Asakusa)
And the like. As used herein, the concept of the term “particle” includes, for example, microspheres having an average particle diameter of about 1 nm to 10 μm, which constitute a polymer emulsion, a latex, and a polymer suspension, as well as an average particle diameter of 10 μm to 100 m.
m particles. However, in the present invention, particles having an average particle diameter of about 100 μm to 25 mm are a general mode.

As described above, the term “particle” used in the present specification is not necessarily equivalent to the concept that these terms generally have in polymer chemistry. Are often used for convenience to refer to the essential aspects of heterogeneous systems.

[Higher order particles] In the present invention, the particles may be primary particles or higher order particles. That is,
Even if it is a secondary particle that is an aggregate or aggregate of a plurality of primary particles, even if it is a tertiary particle that is an aggregate or aggregate of a plurality of secondary particles, an aggregate of a plurality of tertiary particles Or, even if it is a quaternary particle that is an aggregate, or even a higher order particle, there is no particular limitation as long as the effects of the present invention are exhibited.

[Particles Having a Core / Shell Structure] The terms "core", "shell" and "core / shell" as used herein completely describe the concept these terms generally have in polymer chemistry. Inclusive, but not necessarily equivalent. For example, the “core / shell” particles according to the present invention include embodiments in which the “core” is at least partially enclosed in the “shell”. Thus, as used herein, “core”, “shell” and “core /
The term "shell" often refers to the essential aspects of the heterogeneous systems of the polymers according to the invention, although they are not necessarily equivalent to the concepts these terms generally have in polymer chemistry. Shall be used for convenience.

In polymer chemistry, generally,
The term “core” is “core, center, n
ucleus) "," core (center) "
And "seed" are used interchangeably, and the term "shell" is used to refer to "shell, s
kin, husk), "sheath" and "robe". Therefore, the terms “core” and “shell” as used herein shall be used equivalently.

[Structure of Particle] Examples of the core / shell structure include the following embodiments.
However, it is not limited only to these. . A typical core / shell embodiment in which the core particle surface is covered with a shell. . An embodiment of the structure in which the shell is partially deposited on the surface of the core particle and is not completely covered. . A so-called "salami structure" in which a plurality of core particles are sealed by a shell and the cross section is salami sausage. . An embodiment in which the core particles are hollow particles. . An embodiment in which the core particles are porous particles and the material constituting the shell does not fill the voids of the porous particles. . An embodiment in which the core particles are porous particles, and at least a part of the voids of the porous particles is filled with the material constituting the shell. . An embodiment in which the core particles are porous particles, and at least a part of the voids of the porous particles are covered with the material constituting the shell without being filled, and a void phase is present.

The particles of the present invention may be coated on the entire surface of the core phase or may be partially coated as long as the desired function can be substantially achieved. When the area covered by the shell phase on the surface of the core phase is increased, functions such as prevention of stickiness and sustained release of the active ingredient are enhanced. On the other hand, the expression of water absorption of the crosslinked polyamino acid itself becomes more remarkable when the covering area is smaller. The area covered by the shell phase may be appropriately determined according to the characteristics of the material forming the shell phase, the intended use, and the like.

The particles of the present invention may have a single shell phase or a multilayer shell phase as long as the desired function can be substantially exhibited. If the shell phase is a multilayer, prevention of stickiness, enhanced expression of functions such as sustained release of the active ingredient,
Other functions can be provided. On the other hand, if the number of shell phases is one, the expression of water absorption of the crosslinked polyamino acid itself becomes remarkable. The number of layers of the shell phase may be appropriately determined according to the characteristics of the material forming the shell phase, the intended use, and the like.

The core portion and the shell portion may be completely separated from each other, or the shell portion may penetrate the core portion. Further, a gas phase may be contained between the core phase and the shell phase.

The core phase of the particles of the present invention contains a crosslinked polyamino acid. The core phase may be composed of a cross-linked polyamino acid alone, and the particles of the present invention also have a function of sustained release of useful components, and may contain other useful components as necessary. Other useful ingredients include, for example, moisture, bulking agents,
Pigments, UV absorbers, antioxidants, antifungal agents, fragrances, deodorants, organic fertilizers, biological fertilizers, chemical fertilizers, compost, chicken dung, organic materials, pH adjusters, surfactants, foaming agents, corrosive substances, Mineral powders with improved water retention and fertility (bentonite, zeolite powder, etc.), pesticides (pesticides, fungicides, herbicides, fungicides, etc.), plant revitalizers, plant life-extending agents, insect and animal repellents, Soil penetrant, 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, shirasu balloon, inorganic particles such as glass beads, synthetic resin pellets, beads, coarse particles,
Examples include wood chips, wood flour, sawdust, cereal flour, crushed plant shells and stems, plant seeds, useful fungi, and antimicrobial agents. 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.

The fertilizer which is a useful component is not particularly limited.
What is necessary is just to select according to the target plant and construction method. Specific examples include ammonium sulfate, urea, lime nitrogen, salt ammonium, ammonium nitrate,
Molten potassium, potassium sulfate, potassium chloride, potassium nitrate, potassium bicarbonate, ammonium monophosphate, ammonium diphosphate, lime superphosphate, peridotite, perlite, slaked lime, quicklime, molten phosphorus, heavy phosphorus, calcined phosphorus, Magnesium sulfate, magnesium hydroxide, magnesium carbonate, calcium silicate, calcium carbonate, bone meal, potash, IB, CDU, UF, clay
Mixed phosphorus fertilizer, borate fertilizer, fish manure, vegetable oil cake, organic fertilizer, ordinary chemical, urea sulfurated phosphorus with urea, IB phosphorus potassium, ammonium phosphate nitrate, potassium urea sulfurated phosphorus with urea, IBCDU phosphorus phosphorus, ammonium chloride, bitter Phosphorus ammonium salt, phosphorous ammonium salt, phosphoric acid phosphorus, phosphoric acid phosphorus, sulfuric acid phosphorus, phosphoric acid phosphorus, phosphorous acid phosphorus, magnesium sulfate phosphorus, urea phosphorus phosphorus, magnesium urea phosphorus sulfurate, nitrate Phosphorus, Phosphorus urea, Phosphorus ash, Phosphorus ash, Phosphate ash, Phosphorus ash, Phosphorus nitrate-based advanced chemicals, Potassium phosphate-based advanced chemistry, Organic chemicals Fertilizers, chemical conversion with magnesium, and coated fertilizers. The form is not particularly limited, and examples thereof include granules, powders, and aqueous solutions.

The pesticide which is a useful component is not particularly limited.
What is necessary is just to select according to the target plant and construction method. Specific examples thereof include PCP granules, PCP mixed granules, and 2.4.
PA granules, 2.4PA mixed granules, MCP granules, MCC-
MCP granules, MCPB granules, MCPCA granules, CNP granules, CNP-MCP granules, DBN granules, CAT granules, promethrin granules, promethrin-MCPB granules, simethrin granules, simethrin mixed granules, triflularin Granules,
Benthiocarb granules, Benthiocarb-Simethrin granules, Benthiocarb-CNP granules, NIP granules, NIP
-Herbicides such as MCP granules, molinate-simethrin granules, and chlorates; dimethoate granules, ethyl thiometon granules, ethyl thiomethone mixed granules, DEP granules, MPP granules, diazinon granules, diazinon mixed granules, Cartap Insecticides such as granules, Cartap mixed granules, clofenamidine granules, and clofenamidine mixed granules; nematicides such as DCIP granules and DBCP granules; fungicides such as IBP granules; Can be

Specific examples of useful cells which are useful components include VA mycorrhizal fungi, rhizobia, Pseudomonas, Bacillus and the like.

Specific examples of useful antimicrobial agents include, but are not limited to, captan, gliodin, benate, thiobendazole, amicar, biocide, kasugamycin,
Griseofulvin, polyoxin and the like.

Specific examples of useful plant hormones include auxins which promote rooting and callus formation of 2,4-dichlorophenoxyacetic acid, naphthaleneacetic acid, indoleacetic acid and the like; kinetin, zeatin, impentenyladenine, benzyladenine. Cytokinin that promotes the differentiation of buds and the like. 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.

Specific examples of useful minerals include calcium, magnesium, lithium, strontium, barium, and aluminum. These are not particularly limited, but are used in the form of, for example, carbonate, sulfate, acetate, nitrate, oxalate, phosphate, hydroxide, chloride, bromide, iodide, and the like.

Further, in order to form particles or to disintegrate the particles, and to improve the stability and handling of the particles, carriers, disintegrants, excipients, molding aids, extenders, lubricants Agents, reinforcing agents, plasticizers, dispersants, wetting agents, lubricants, coloring agents, foaming agents, defoamers, antistatic agents, charge control agents, fragrances, stabilizers, buffers, water repellents, desiccants And various optional components such as a water-soluble carrier, a mineral carrier, and a solvent.

Specific examples of the carrier which is an optional component include limestone clay, kaolin, sericite, ziglite, talc, bentonite, acid clay, calcium carbonate, silica, silica sand, diatomaceous earth, pumice, zeolite, perlite, Vermiculite, slaked lime, urea, ammonium sulfate, salt ammonium, chemical fertilizer, plastic foam, slag, fly ash, bran, bran, rice husk, sawdust, wood flour, pulp floc, soy flour, corn stalk, nut hull, fruit kernel And the like.

Specific examples of the optional disintegrant include:
When used for pharmaceutical applications, agar, starch, hydroxypropyl starch, sodium alginate, carboxymethyl starch ether, gum arabic, tragacanth, gelatin, casein, cellulose, carboxymethylcellulose, calcium carboxymethylcellulose, tween, pluronic, sodium laurate, carboxy Rick resin, etc., when used in agricultural and horticultural applications, ammonium sulfate, potassium chloride, salt, bentonite, urea, anionic surfactants, etc., when used in food applications, salt, sodium glutamate, sodium inosinate ,dextrin,
Starch, agar and the like.

The various additives mentioned above are preferably biodegradable from the viewpoint of environmental protection. Also, if necessary, a water-absorbing resin other than the crosslinked polyamino acid is used for the core phase,
It may be used in combination with a crosslinked polyamino acid.

Further, a binder may be used in the core phase, if necessary. Specific examples of the binder include fully fermented oil residue, clay, gelatin, gum arabic, acacia powder, polyvinylpyrrolidone, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, dextrin, starch, sodium alginate, acrylate latex, and styrene. Butadiene-based latex, vinyl acetate-based latex, acrylic acid-acrylamidepropanesulfonamide-copolymer, partially saponified polyvinyl alcohol, dioctyl phthalate, and the like. These binders preferably have biodegradability from the viewpoint of environmental protection.

The core phase may contain a surfactant (or a soil penetrant). The surfactant (or soil penetrant) is not particularly limited. Specific examples thereof include alkyl sulfates such as sodium lauryl sulfate, triethanolamine lauryl sulfate, and ammonium lauryl sulfate; polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate and triethanolamine polyoxyethylene lauryl ether sulfate; Salts; alkyl sulfonates such as sodium lauryl sulfonate, potassium lauryl sulfonate, triethanolamine lauryl sulfonate, ammonium lauryl sulfonate, sodium stearyl sulfonate; alkyl diphenyl ether disulfonates such as sodium dodecyl diphenyl ether disulfonate; dodecyl benzene Alkyl aryl sulfonates such as sodium sulfonate; sodium dodecyl naphthalene sulfonate Alkyl, naphthalenesulfonic acid such as sodium salt of β-naphthalenesulfonic acid formalin condensate; dialkylsulfosuccinate such as ligninsulfonic acid salt, sodium distearylsulfosuccinate, sodium dioctylsulfosuccinate; polyoxyethylene lauryl ether acetic acid; Polyoxyethylene alkyl ether acetates such as sodium oxyethylene lauryl ether acetate; alkali metal salts of a copolymer having a carboxyl group such as alkylene maleic acid copolymer; coconut oil fatty acid, palmitic acid, behenic acid, lauric acid, stearin Acid, myristic acid, oleic acid, sodium laurate, potassium laurate, triethanolamine laurate, ammonium laurate, sodium stearate, potassium stearate Fatty acids or salts thereof such as sodium, triethanolamine stearate and ammonium stearate; monoalkyl phosphates such as sodium lauryl phosphate, triethanolamine lauryl phosphate and ammonium lauryl phosphate; No. In addition, lauryl alcohol, myristyl alcohol, cetanol, cetostearyl alcohol,
Higher alcohols such as stearyl alcohol, 2-octyldodecanol and behenyl alcohol; glycerin,
Polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, sorbitol, sorbitan, and pentaerythritol; polyoxyethylene lauryl ether, polyoxyethylene cetyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene higher alcohol ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl dodecyl phenyl ether, polyoxy Polyoxyethylene alkyl phenyl ether such as ethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether, polyoxyethylene styryl phenyl ether, polyethylene glycol monostearate, polyethylene glycol distearate, ethylene glycol distearate, polyoxyethylene hydrogenated castor oil, etc. A polyoxyethylene alkyl ester of
Copolymers of polyoxyethylene glycol and polyoxypropylene glycol such as polyoxyethylene polyoxypropylene glycol; sorbitan monolaurate;
Sorbitan alkyl esters such as sorbitan monostearate, sorbitan monooleate, sorbitan monopalmitate, sorbitan sesquioleate, sorbitan coconut oil fatty acid, sorbitan monopalmitate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate; Polyoxyethylene sorbitan monolaurate, sorbitan polyoxyethylene coconut oil, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate,
Polyoxyethylene sorbitan alkyl esters such as polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan triisostearate; tetraalkyl esters such as polyoxyethylene sorbite tetraoleate Fatty acid polyoxyethylene sorbit; glyceryl monostearate,
Glycerin alkyl esters such as 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; lauric acid diethanolamide And nonionic surfactants such as alkyl alkanolamides. Alkylamine salts such as coconut amine acetate and stearylamine acetate; alkyltrimethylammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and cetyltrimethylammonium chloride; distearyldimethylammonium chloride and dialkyl (12-18) dimethyl chloride Cationic surfactants such as dialkyldimethylammonium salts such as ammonium; benzalkonium salts such as benzalkonium chloride; and the like. Furthermore, alkyl betaines such as lauryl betaine and stearyl betaine; alkyl dimethyl amino acetate betaines such as lauryl dimethyl amino acetate betaine and stearyl dimethyl amino acetate betaine; 2-alkyl-N-
Alkyl carboxymethyl hydroxyethyl imidazolinium betaine such as carboxymethyl-N-hydroxyethyl imidazolinium betaine; alkyl amide propyl betaine such as lauric amide propyl betaine and coco amide propyl betaine; alkyl hydroxy sulfo such as lauryl hydroxy sulfo betaine Betaine;
And amphoteric surfactants such as alkyldimethylamine oxide such as lauryl dimethylamine oxide.

The shell phase of the particles of the present invention comprises a coating material and / or a resin. The coating material and the resin are not particularly limited as long as they can form a shell phase. The coating material and the resin may contain a substance capable of forming a coating film as a main component, and may contain other useful components as needed. As specific examples of the components contained in the shell phase as necessary, the various components described above as specific examples of useful components and optional components of the core phase can be similarly mentioned.

Specific examples of the hydrophilic coating material for forming the shell phase include starch, soluble starch, dextrin, pregelatinized starch, alginic acid, sodium alginate, arabia gum, tragacanth gum, locust bean gum, casein, sodium caseinate, gelatin , Niwa, soy protein and other hydrophilic natural products; sodium carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, sodium ligninsulfonate, calcium ligninsulfonate, sodium carboxymethylstarch, hydroxyethylstarch, sodium starch phosphate, hydroxypropylcellulose, Hydrophilic semi-synthetic products such as hydroxypropyl methylcellulose; polyvinyl alcohol, polyvinyl methyl ether, polyacrylamide, polya Sodium acrylic acid, polyacrylamide propylsulfonic acid, polyethylene glycol,
Hydrophilic synthetic products such as polyethylene oxide, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers and copolymers thereof; nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. Surfactants; sodium silicate; glycerin; and the like. As specific examples of these surfactants, various surfactants mentioned above as specific examples of surfactants that may be contained in the core phase can be similarly mentioned.

Specific examples of the hydrophobic coating material for forming the shell phase include shellac, rosin, tall oil,
Hydrophobic natural products such as animal and vegetable oils, 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,
And hydrophobic synthetic products such as petroleum resins and phenolic resins.

Specific examples of the resin for forming the shell phase include vinyl chloride resin, vinyl acetate resin, vinylidene chloride resin, high density polyethylene, low density polyethylene, polypropylene, acrylic resin, ABS resin, polystyrene resin, and styrene resin. , Polyamide resin, acetal resin, polycarbonate resin, polyester resin and the like. Further, there may be mentioned those which become thermosetting resins after molding, such as phenol resins, urea resins, melamine resins, unsaturated polyester resins, epoxy resins and polyurethane resins. Furthermore, when used for agricultural and horticultural purposes, it is generally difficult to recover the same, so it is preferable that the shell phase also has biodegradability. From such a viewpoint, for example, biodegradation of polylactic acid, polylactide, polybutylene succinate, polycaprolactone, polyhydroxybutyrate, polyhydroxyvalerate, polyglycolic acid, polyamino acid, polysuccinimide and copolymers thereof, and the like It is preferable to use a conductive polymer. Typical examples of the biodegradable polymer include aliphatic polyesters and polysuccinimides. Specific examples of the aliphatic polyester include (co) polyhydroxycarboxylic acids such as (co) polylactic acid.

The shell phase may or may not have a water vapor barrier property as long as the desired function can be exhibited. In the case of a shell layer having poor water vapor barrier properties, the particles themselves increase in weight due to moisture absorption, but if the shell phase itself is not sticky due to moisture absorption, stickiness may be prevented in some cases. Further, even if water vapor permeates, the molecules of the useful component are often not permeated because the molecules are large, and the useful component is blocked by the shell phase, and may be useful in terms of sustained release.

Further, in the crosslinked polyamino acid-containing particles of the present invention, if a hydrophobic shell phase is formed on the surface of the inherently hydrophilic crosslinked polyamino acid-containing particles by using a coating material, for example, the particles are in contact with water. Even when the surface does not immediately start absorbing water, the particles are dispersed in water, and the particle aggregate becomes isolated particles. After that, each particle absorbs water and swells, so that "mamako" hardly occurs. In addition, for example, even when a hydrophilic coating material is used, if a surfactant is further used as a coating material, a favorable effect can be obtained because the hydrophilic group of the surfactant faces inward and the hydrophobic group faces outward. .

The ratio of the shell phase and the ratio of the crosslinked polyamino acid in the whole particles may be appropriately set to optimal values according to the intended function of the shell phase. Generally, when the shell phase is too small, the function expression of the shell phase becomes weak,
If it is too large, the water absorption rate and water retention may decrease. Usually, the amount of the shell phase is about 0,0% based on the total weight of the particles.
The amount of the crosslinked polyamino acid is preferably 1 to 99.9% by weight, more preferably 10 to 99% by weight, based on the weight of the whole particles.
Is more preferred.

The shape of the particles of the present invention is not particularly limited. It may be formed by tabletting, or may be of irregular shape obtained by pulverization, crushing, or dry granulation. The size of the particles of the present invention is not particularly limited, and may be changed according to the intended use and intended purpose. For example, when used as a soil conditioner such as a water retention material for agriculture and horticulture, the average particle size is preferably from 10 to 10,000 µm, more preferably from 100 to 5000 µm. When used as a sanitary material, its average particle size is 1 to 5000
μm is preferable, 10 to 1000 μm is more preferable,
100 to 500 μm is particularly preferred.

(4) Method for Producing Crosslinked Polyamino Acid-Containing Particles The method for producing crosslinked polyamino acid-containing particles is not particularly limited. For example, (4-1) a step for producing core particles (particles serving as a core phase); 4-2) A method including a step of forming a shell phase by coating core particles.

(4-1) Step of Producing Core Particles The method of producing core particles is not particularly limited.
For example, a previously produced cross-linked polyamino acid is ground and / or
Alternatively, there are a method of using granules, a compression granulation method, and a method of molding using a binder. Alternatively, desired particles can be formed by using a thermoplastic resin as a binder, melting the resin by heating, and cooling the resin. Further, various methods described in a granulation handbook (Ohm Co., published in 1975, edited by Japan Powder Industry Association) can be used.

The compression granulation method is not particularly limited. For example, tableting, briquetting, or even
Compacting obtained by crushing the molded product obtained by these methods can be mentioned. The shape of the obtained compression molded product (the shape of the core particles) is not particularly limited as long as it can finally form the core phase, and can be selected as needed. As a specific example of the shape, in the case of tabletting, a round shape,
Football type, triangular type, square type, rectangular type, hexagonal type, ring type, etc. are mentioned, and the plane is goishi type, flat type edge,
A flat type, a convex type, a concave type, a ring type and the like can be mentioned. In briquetting, sheet-like, plate-like, pillow-type, lens-type, almond-type, prism-type, rod-like, corrugated sheets and the like can be mentioned. In compacting, a crushed shape or the like can be given. The size of the compression molded product is not particularly limited, either, and can be selected according to the intended use.

The particle size of the raw material used for tabletting and briquetting is not particularly limited, and varies depending on the material used, such as the polyamino acid and other additives. Generally, it is better to use a powder having a wide particle size distribution, such as fine particles mixed in coarse particles,
A strong compression molded product is obtained. When a powder composed of fine particles is used, 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 fixed amount of the raw material powder into the mortar, to keep the size of the obtained compression-molded product constant, and to increase the productivity, the dispersion of the powder density is required. Preferably it is not present. For this purpose, it is preferable that the raw material powder is sieved in some cases to adjust the particle size, or to adjust the particle size by performing a granulation operation in a previous stage.

In the tabletting and briquetting, a plasticizer may be added in some cases. If plastic powder is used, plastic deformation is easily caused by compression, the contact surface between the particles becomes large, and no elastic strain remains in the molded product even after the compressive force is removed, so a strong molded product can be obtained. can get.

It is preferable that the surface of the raw material powder is not contaminated by steam, gas, oxide film and the like. Therefore, for example, it is preferable to form a clean fractured surface by crushing the particles immediately before molding and then compression-molding, since a strong molded product can be obtained.

In the tabletting and briquetting, a binder may be added in some cases. The use of a binder facilitates molding when a large amount of porous powder such as ore or coke having high hardness is used as a component other than the polyamino acid. Specific examples of the binder include clay, asphalt, Portland cement, wax,
Matrix-type binders such as paraffin, sugar, starch, gilsonite, and coal tar pitch; film-type binders such as water, molasses, pulp waste liquor, sodium silicate, starch, pitch emulsion, polyvinyl alcohol, and bentonite; . Further, a reactive binder which forms a chemical bond between binder components or between a binder and other raw material powders is also included.

When the raw material powder used for tabletting and briquetting contains two or more components, it is preferable to sufficiently mix them before compression molding. The equipment used for mixing is not particularly limited, and examples thereof include an edge runner mill and an Erich mixer.

In tabletting and briquetting, a lubricant may be added in some cases. 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. Can be increased. Lubricant, even if it is an internal lubricant used after mixing with the raw material powder before molding, die,
An external lubricant which is used by being applied to a roll surface or the like may be used. Specific examples of the lubricant include water, lubricating oil, glycerin, silicon, graphite, talc, magnesium stearate, molybdenum disulfide, ethylene glycol, paraffin and the like.

In the tableting, 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.

Examples of the compressor used for compression molding include a tableting machine and a briquetting machine. Specific examples of the tableting machine include a single-shot tableting machine, a rotary tableting machine, a one-point compression type machine, a multi-point compression type machine, a cored tableting machine, a multi-layered tableting machine,
Inclined roll-type tablet presses and the like can be mentioned. In addition, compression molding can be classified into wet granule compression, dry granule compression, direct powder compression, and the like from the viewpoint of the production process.

A molding method using a binder, which is one of the methods for producing core particles, includes a method of binding using a binder and a solvent, and a method using a thermoplastic resin as a binder. There is a method in which a resin is melted by heating and then molded by cooling. When a hydrophilic binder is used, water is used as a solvent, and when a hydrophobic binder is used, an organic solvent is used. As the organic solvent, those which are easily removed and have high safety are preferable. Examples include acetone, methanol, ethanol, isopropanol, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride and the like. When the binder itself is a liquid, a solvent may not be required in some cases.

The binder is not particularly limited. Specific examples thereof include the various components described above as specific examples of the coating material for forming the hydrophilic and hydrophobic shell phases. Further, an adhesive having higher adhesiveness than a normal binder may be used. Adhesives include a solvent type and a reaction type which reacts during molding to cause crosslinking and the like.

The granulation method used in the method for producing the core particles is not particularly limited, but an extrusion method is preferred.
That is, this is a method in which a solvent is added to powder or granules as raw materials, mixed, and the mixture is extruded by a suitable extruding mechanism to extrude the mixture from holes of a screen, a die, or the like, thereby granulating the mixture. The machine used here is not particularly limited. Specific examples thereof include a pre-extrusion extrusion granulator, a lateral extrusion extrusion granulator, a vacuum extrusion extrusion granulator, a screw extrusion granulator such as a pre-treatment combined extrusion granulator, and a cylindrical die horizontal. Roll-type extrusion granulators such as extrusion-type extrusion granulators, cylindrical-type dies, vertical-type extrusion-granulators, disk-type dies, horizontal-type extrusion-granulators; basket-type extrusion-granulators, oscillating-type extrusion-granulators, etc. Blade-type extrusion granulators; self-molding extrusion granulators such as gear-type extrusion granulators and cylinder-type extrusion granulators; ram-type extrusion granulators such as intermittent-type extrusion granulators and continuous-type extrusion granulators Granulator; and the like.

The particle size of the raw material used here is not particularly limited, and may be selected according to the purpose of use. However, the particle size is preferably such that it can easily pass through the holes of the die and that the mixing is uniform. Generally, fine powder of 100 to 200 mesh or less is preferred.

When the production of the core particles is carried out by a dry method,
The raw material preferably has fluidity. Further, it is preferable that the raw material has plasticity exhibiting a thixotropic phenomenon. In some cases, it is preferable to add an excipient or a binder for those exhibiting the dilatancy phenomenon. Examples of binders include acetone, methanol, ethanol, gum arabic, sodium alginate, hydroxypropylcellulose, methylcellulose, sodium caseinate, glycerin, corn starch, sodium carboxymethylcellulose, gelatin, dextrin, starch, molasses, lactose, polyvinyl alcohol, polyvinyl Pyrrolidone, microcrystalline cellulose, pitch, sodium polyacrylate,
Examples include 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 is not particularly limited, but a mixer such as a kneader can be used. Also,
The method of liquid addition is not particularly limited, and may be determined as desired.

The post-processing step for the production of the core particles is not particularly limited, but it is preferable to carry out sizing. Examples of a method for sizing include a crushing sizing method and a spherical sizing method.

The core particles 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, and from 40 ° C to 12 ° C.
0 ° C. is more preferred. Further, crushing, crushing, sieving and the like may be performed.

When a thermoplastic resin is used as a binder and the resin is melted by heating and then molded by cooling, the thermoplastic resin is not particularly limited. Softens and melts and becomes solid again when returned to room temperature.In addition to ordinary thermoplastic resin, it shows plasticity during molding, but once heat is applied, crosslinking occurs between molecules due to heat, crosslinking agent, etc. , A resin that is cured after molding or during molding to become a thermosetting resin. Here, both are referred to as a thermoplastic resin. As specific examples of the thermoplastic resin, various resins described above as specific examples of the resin for forming the shell phase can be similarly mentioned.

In general, if the amount of the thermoplastic resin used is too small, the effect as a binder is lost, and if the amount is too large, the sustained release and effect of the active ingredient are reduced.
In particular, it greatly affects the sustained release of the active ingredient. Although the amount of use is not certain, it is preferably 5 to 90% by weight, particularly preferably 10 to 80% by weight in the core particles. In addition to the polyamino acid and the thermoplastic resin, a plasticizer, a stabilizer, a lubricant, a coloring agent, a reinforcing agent, an extender, and the like may be added to the core particles as needed.

The specific steps in this method are not particularly limited, but generally comprise mixing, kneading, granulating and dehydrating and drying steps. Examples of the mixer include a mixer such as a ribbon blender, a Henschel blender, and a drum blender. Examples of the kneading machine include a mixing roll, an intensive mixer, a short-screw extruder, and a high-speed twin-screw continuous mixer. Examples of the granulating device include a cold cut device such as a sheet cut method and a strand cut method, and a hot cut method device 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.

(4-2) Step of coating core particles One of the important features of the particles of the present invention is that the particles of the present invention have a shell phase containing a coating material and / or a resin on the surface of the core particles. One. The shell phase can be preferably formed by applying a coating material solution or a coating material in a molten state, or a resin solution or a resin in a molten state to the surface of the core particles. Here, the coating material refers to a substance capable of forming a film. Specific examples of the coating material and the resin are as described above.

As a specific example of the solvent in which the resin is dissolved, in the case of using a binder and a solvent in the production of the core particles to bond the resin, the solvent may be the same as the specific examples given above. it can. The viscosity of the liquid for coating is not particularly limited, but when spraying from a nozzle or the like, it is preferable that the viscosity be such that it can be sprayed smoothly. In the case of a suspension, the liquid can be supplied to the core particles while being mixed by an operation such as stirring.

The method for coating the core particles is not particularly limited, and any commonly used method can be used. For example,
Pan coating method, fluid coating method, dry coating method, belt type electrostatic coating method, dipping method, drum method,
Ring method and the like can be mentioned.

The pan coating method is a method in which a coating agent is sprayed or dropped while a substance to be coated is rotated in a coating pan, and the solvent is removed by drying. The material of the coating pan is not particularly limited, and examples thereof include copper, stainless steel, and plastic. Also, the shape of the coating pan is not particularly limited, and may be a pier type, an onion type,
Conical type and the like can be mentioned. A baffle may be attached to the bread to help stir. The position, size, quantity, etc. of the baffle are not limited. The size is not limited, and a diameter of several tens cm to several meters can be used. The supply method is not particularly limited. It may be supplied by spraying or supplied as droplets. As the spraying method, a method using an air spray, an airless spray, or the like can be given. The air spray uses a two-fluid nozzle and atomizes the coating liquid with compressed air around the nozzle. In the airless spray, a pressure of several Pa to several tens Pa is applied to a solution or a suspension to atomize the solution or the suspension. The particle size, pattern and amount of the sprayed mist are not particularly limited.

The fluid coating method is a method in which particles are suspended and suspended in a spouted bed, a fluidized bed, and a transport layer. For example, from the bottom of the packed bed of solid particles,
The coating is performed in a fluidized bed state in which a gas flow is supplied to keep the particles in a dynamic suspension state, or a spouted bed state in which the gas flow is blown from the bottom of the cone. Particles are usually blown up in the center, descend and circulate near the peripheral wall. The flow rate of the spray and the temperature in the system may be appropriately selected depending on the solution or suspension to be used. The particle size of the core particles to be coated may be large enough to be in a floating state.
For example, a diameter of about 1 mm is preferable. The number, position, and direction of the nozzles to be sprayed can be changed according to the target coat.

The dry coating method is a method in which granules for coating are coated on the surface of tablets by a dry method using a special tableting machine (pressed tableting machine). After tableting the core tablet, coating may be performed using the same tableting machine.After forming the core tablet in another tableting machine, the core is supplied to a cored tableting machine. The outer layer may be dry-coated. The method of placing the core material is to drop the nucleus from the transfer plate at the point where the center of the nucleus transferred by the nucleus transfer device is synchronized with the center of the mortar, but gradually set the nozzle that sucks the nucleus in vacuum. There is a method in which the nucleus is implanted in a mortar. If the coating layer is too thin, the coating layer cannot withstand the expansion of the core after compression molding, which may cause capping and lamination. Conversely, if the coating layer is too thick, the product may crack. The difference between the diameter of the coating layer and the core is 2 mm when the core is 8 mm or less.
As described above, when the core is 8 mm or more, 3 mm or more is preferable. The radius of curvature of the coating layer is preferably at least 1.1 times the radius of curvature of the core surface, and particularly preferably 1.5 times. The particle size distribution of the core is preferably narrow, not including coarse particles and fine powder,
It is preferable to include fine granules at an appropriate ratio to fill the space between the large particles.

The belt type electrostatic coating method is a method in which particles serving as nuclei are arranged on a belt, a coating liquid is atomized by a sprayer, and the mist is passed between high voltage grids to coat the surfaces of the core particles.

The immersion method is a method in which core particles are immersed in a coating solution, pulled up and dried.

(5) Water retention and sustained release of drug in crosslinked polyamino acid-containing particles One of the effects of the particles of the present invention is the sustained release of active ingredients such as drugs. However, it is very useful even in applications where sustained release is not necessarily required, such as water retention materials for agricultural and horticultural use. This is because the particles of the present invention also have an effect of preventing stickiness, that is, an excellent effect of preventing deterioration of workability due to moisture absorption or absorption of moisture contained in soil.

The required water retentivity, the timing of developing the water retentivity, and the sustained release of the drug differ depending on the use and purpose of using the particles of the present invention. Water retention is required for a certain period of time, and in some cases, it is preferable that water retention be eliminated after a certain period of time. Also,
In the case of a resin having an excessively high water retention, such as a crosslinked polyacrylic acid-based resin, root rot is likely to occur, and water in the gel cannot be effectively used by plants under drying. On the other hand, the particles of the present invention do not cause root rot of the plant, and the plant can effectively use the water in the gel even under dry conditions.
There is no particular limitation on when the water retention occurs, but it can be adjusted as appropriate by changing the type of resin contained in the shell phase (coat layer), the thickness of the shell phase, and the like.

In general, when the resin contained in the shell phase has high hydrophilicity, the water-absorbing property is rapidly developed, and when the resin is highly hydrophobic, the water-absorbing property is slowly developed. In addition, the permeability of water vapor also affects the development of water absorption, and a resin having a high water vapor barrier has a low development of water absorption. Furthermore, when the shell phase is thick, the biodegradability or degradability rate and manner of the resin also affect the development of water absorption. If the biodegradability of the resin is fast, the expression of water absorption is fast, and if it is slow, it is slow. When the decomposition occurs from the surface and is hard to occur inside, the expression of water absorption is slow, and when the decomposition including the inside occurs like a hydrolyzable resin, the expression of water absorption is fast.

The larger the amount of the crosslinked polyamino acid in the particles, the higher the water retention, and the smaller the amount, the lower the water retention. However, the amount used has a balance with the sustained release of the drug.
I can't say it. Generally, the amount of cross-linked polyamino acid is preferably from 1 to 80% by weight, based on the weight of the whole particles,
0 to 50% by weight is more preferred. However, when emphasis is placed on water retention, the content is preferably 50 to 100% by weight, and 60 to 100% by weight.
100% by weight is more preferred.

Regarding the sustained release properties of the particles of the present invention, 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 time, when it is desired to maintain a certain amount of effect for a certain period, or after a certain period of time, It can be controlled to be effective in any case where expression is desired. The method of controlling the sustained release depends on the polyamino acid or the content thereof, the active ingredient, the molding method, the strength of the molded product, the additive, or the content thereof.

The sustained release of the polyamino acid varies depending on the affinity between the polyamino acid and the active ingredient and the degree of gelation of the polyamino acid. Since the polyamino acid has high hydrophilicity, the active ingredient having high hydrophilicity has high affinity with the polyamino acid gel and is hardly released. On the other hand, active ingredients having high hydrophobicity have low affinity and are easily released. In addition, when the polyamino acid is in a gel state and has a high swelling ratio, it is easy to release a drug. When the amount of the polyamino acid is increased, the disintegration of the whole particles is promoted, so that the sustained-release becomes faster. On the other hand, when the amount of the polyamino acid is small, the disintegration is controlled by other components. In general, the release period is short when the active ingredient has high hydrophilicity, and the sustained release period is long when the hydrophobicity is high or the solubility in water is low. Regarding the difference in sustained release due to the molding method, it can not be decided unconditionally because it is strongly affected by other factors, but as a general tendency, the sustained release of compression molded products was performed in a short period of time, and it was reprocessed Some have a longer sustained release period. The product produced by extrusion granulation or the like using a binder has 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 influence the sustained release.

(6) Use of the Crosslinked Polyamino Acid-Containing Particles The use of the crosslinked polyamino acid-containing particles of the present invention is not particularly limited. For example, agriculture and horticulture, medicine, food, bath additives,
It can be used as a water-absorbing resin for various uses such as sanitary materials. In particular, it is very useful for sanitary materials and soil conditioners. Further, the most effective use of water retention and sustained release of chemicals is the use of a soil conditioner for agricultural and horticultural use.

(7) Composition of Soil Composition Containing Cross-Linked Polyamino Acid-Containing Particles In agricultural and horticultural applications, a soil composition obtained by mixing the cross-linked polyamino acid-containing particles of the present invention with soil as a soil improver is very useful. is there. Examples of the soil used in the soil composition 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, and kea sand. And earth, vermiculite, charcoal,
Hyuga clay, clay and the like. In addition, soils such as fields and sands to which the soil composition is applied, or other soils can also 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 form of the soil used for preparing the soil composition is not particularly limited as long as it can simultaneously exert substantially sufficient water retention and ventilation effects when the soil composition is prepared. However, it may be granular. Generally, a particle size of about 5 to 50 mesh (in a dry state) or a particle size of 0.5 capable of expressing coarse pores having excellent air permeability and water permeability.
What granulated to about 5.0 mm (dry state) is preferable. The soil composition may contain various useful components as needed. 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 Small pieces, sawdust, cereal flour, crushed plant shells and stems, plant seeds, fungi, fine radioactive minerals such as Ferguson, far-infrared radioactive ceramics, Otani stone,
Ethylene gas-absorbing minerals such as zeolite, perlite,
Examples include inorganic water retention materials such as pumice and vermiculite, and water-absorbing resins other than crosslinked polyamino acid resins. The useful component to be added preferably has biodegradability from the viewpoint of environmental protection. Many of the above-mentioned useful components have a rapid effect in many cases.

[0098] The soil composition may be solidified 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 crosslinked polyamino acid-containing particles The method of use and place of use are not particularly limited. For example, there are a method of spraying a molded product or a soil composition on a field as topsoil, and a method of using it as a culture soil for a nursery or 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, particles or water,
As a gel swollen with liquid fertilizer, etc., a method of burying a predetermined amount in the soil, a method of spraying or burying those solidified with a binder in the field, a method of including them in molded seedlings and transplanting them with plants, The method of mixing while plowing the soil may be used. In addition, the state of the plant can be used in a wide range, and is not particularly limited as long as the plant grows,
For example, it can be used to germinate seeds, grow seedlings, grow leafy vegetables, fruits and vegetables, root vegetables, flowers, etc., and replant adult trees.

(9) Sanitary Material Containing Cross-Linked Cross-Linked Polyamino Acid-Containing Particles The cross-linked polyamino acid-containing particles of the present invention are not limited in terms of type, shape, size and style, and are suitable for generally used sanitary articles. Used for In particular, it exerts excellent effects on the treatment of waste and the properties of sanitary articles.

The types of sanitary articles include, for example, children's paper diapers, adult paper diapers, sanitary napkins, tampons, panty liners, sanitary sheets, incontinence pads,
Medical blood absorbers and the like. As described above, the crosslinked polyamino acid-containing particles of the present invention can be used for any particles that require a function as an absorber.

The structure of the sanitary ware is not particularly limited, and may be a structure used for general sanitary ware, and its size can be selected according to the type, shape and style of the sanitary ware to be used. These are generally based on consisting of a topsheet, a backsheet and an absorbent core. But,
The sanitary article is not limited to these parts alone, and may include other necessary parts as needed. For example, as disposable diaper products, other parts such as waist gathers, leakage prevention gathers, inner leg gathers, outer leg gathers, frontal tape, adhesive, magic tape, fastener tape systems, release tape systems, Velcro, etc. A mechanical fastener tape system, a liquid diffusion layer, and the like. In addition, the sanitary ware may have a structure without a top sheet and / or a back sheet, if necessary. That is, an essential element of the sanitary article is the absorbent core, and other sanitary articles including the absorbent core are not particularly limited, and the sanitary article can be constructed by combining various parts. Further, one part may have two or more functions at the same time. For example, the absorbing core can have a diffusion function. In addition, composite of top sheet / acquisition layer, end cap / waist gather, release tape / faston tape, composite of top sheet and side sheet, inner leg gather, etc., and composite of back sheet and absorber And a filmless composite.

The sanitary article can have not only a single structure but also a multiple structure. In particular, the absorption capacity can be enhanced by the structure in which the absorption cores are stacked. These may be not only the structure of the entire sanitary article but also the structure of each part in a multiplex structure. For example, not only a structure in which the tissue layer / pulp layer / absorbent resin layer is vertically combined, but also a combination of these can be formed into a multiple structure.

The structure of the absorbent core is made of, for example, pulp and a water-absorbent resin, and may include absorbent paper (diffusion paper) in some cases. The pulp is preferably defibrated pulp.
The absorbent paper is not limited, but is usually a paper mainly composed of cellulose.

The location of the absorbent resin is not particularly limited.
It may be any of the upper layer, the middle layer, and the lower layer of the absorbent core,
It may be mixed with pulp. A structure that can efficiently absorb body fluid and the like is preferable. Further, it is preferable that the water-absorbing resin is dispersed so that its performance can be sufficiently exhibited.
For this purpose, a method of fixing the water-absorbing resin so that the water-absorbing resin is not unevenly distributed during the manufacturing process, the delivery of the product, the storage, or the like may be adopted. For example, a method in which a thermoplastic resin is mixed into pulp and a part thereof is adhered by heat or the like, or a part is adhered by a binder and the like can be mentioned. The binder resin is
Although not particularly limited, it is preferable to use a biodegradable polymer binder in order to express biodegradability, which is one of the objects of the present invention.

The material constituting the sanitary ware together with the crosslinked polyamino acid-containing particles of the present invention is not particularly limited, but a biodegradable polymer is preferable. Examples of the material constituting the top sheet and the back sheet include non-sized paper, nonwoven fabric, water-permeable porous sheets such as polyethylene, polypropylene, hydrophilized polyethylene and polypropylene, cellophane, vinylon film, polyvinyl alcohol (PVA) film, heat A plastic film,
Foamed to have fine communication holes at the time of film production, Fine communication holes formed by adding an inorganic substance or a high-melting nucleating agent and stretching, mixed paper of polyethylene or polypropylene and pulp, paper Laminate with non-woven fabric, size paper or non-woven fabric with cellulose film formed by viscose, cellulose film with fine holes formed, plastic film made of thermoplastic resin, polyethylene paper, metal foil, etc. Part or all of thermoplastic nonwoven fabric, rayon, fibers such as pulp, polyolefin, polyester, nonwoven fabric impregnated or mixed with resin such as polyamide, polyolefin, polyester,
A nonwoven fabric made of a resin such as polyamide is exemplified.

The biodegradable materials constituting the top sheet and the back sheet are classified into non-melting materials and fusible materials. Examples of the non-melting material include pulp, cotton, wool, regenerated cellulose fiber, and solvent-spun cellulose fiber. As a specific example of pulp,
Virgin pulp from wood and pulp recovered from waste paper and the like can be mentioned. Specific examples of the fusible material include aliphatic polyester and aliphatic polyesteramide. Specific examples of the aliphatic polyester include poly (α-hydroxycarboxylic acid) such as polyglycolide and polylactic acid; poly-ε-caprolactone, poly-β-propiolactone, poly-3-hydroxypropionate, poly- 3-hydroxybutyrate, poly-3-hydroxycaprolate, poly-3-hydroxyheptanoate, poly-3-hydroxyoctanoate, and poly-3-hydroxyvalerate, poly-4-hydroxybutyrate Polyhydroxyalkanoates such as copolymers with acrylates; polyethylene oxalate, polyethylene succinate, polybutylene succinate, polybutylene adipate, polybutylene sebacate, polyhexamethylene sebacate, polyneopentyl oxalate and copolymers thereof. Dihydric alcohols such as polymers Condensates of dihydric carboxylic acid; additionally these ones having a urethane bond obtained by chain extension with divalent isocyanate compound; and the like. Specific examples of the aliphatic polyesteramide include a lactone and lactam copolymer such as a copolymer of ε-caprolactone and ε-caprolactam.

[0108]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples. In Examples and Comparative Examples, "parts" means "parts by weight".
Means

(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, then 15 parts of the test sample was added to 800 parts of the inoculum, and the test was carried out at 58 ° C. for 40 days to measure the amount of carbon dioxide generated The amount of carbon dioxide generated relative to the amount of carbon contained in the test sample converted to carbon dioxide was expressed as a biodegradation rate (%). Here, some of the easily biodegradable samples promote the decomposition of even the carbon content in the inoculum, and thus may have a value exceeding 100%.

(2) Measurement of water absorption The water absorption was measured by using the tea bag method for tap water. That is, about 0.03 parts of the water-absorbent resin is put into a non-woven tea bag (80 mm × 50 mm), immersed in an excessive solution to swell the resin for 10 hours, and the tea bag is pulled up and drained for 1 minute. The weight was measured. Further, assuming that a similar operation was performed using only a 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 by the weight of the water-absorbent resin was calculated as the water absorption (g / g). 1 g of resin).

(3) "Mamako" production test A 70 mm diameter petri dish containing 40 g of physiological saline was
200 mg of the water-absorbent resin was added at a time and observed, and those in which "Mamako" was not formed were marked "O", and those in which "Mamako" was formed were marked "X".

(4) Measurement of Water Absorption Rate The measurement of the water absorption rate was performed on tap water by the tea bag method. That is, about 0.03 parts of the water-absorbent resin is put into a non-woven tea bag (80 mm × 50 mm), immersed in an excessive solution to swell the resin for 1 minute, and the tea bag is pulled up and drained for 10 seconds. The weight was measured. The calculation of the water absorption (g / g of resin) is as described above.

(5) Measurement of Moisture Absorption and Stickiness Test by Moisture Absorption Measurement of the amount of moisture absorption was performed by placing one part of the water-absorbent resin in a glass petri dish and absorbing moisture at 23 ° C. and 60 ± 3% humidity (RH) for 20 hours. The change in weight after the heating was represented by an increase in the original weight in%. The stickiness test is 23 ° C, 60 ± 3
% Humidity In a room of constant temperature and humidity under the same conditions, the time when the sample adhered to the container of moisture absorbed on a glass petri dish was measured. That is, the time when the resin did not stick to the container even when the container was tilted by 60 degrees was measured, and the measured time before the time when the resin adhered to the container was expressed as the stickiness. The measurement time was measured every 10 minutes up to 1 hour, every 1 hour after 1 hour, and up to 20 hours. The stickiness due to the absorption of moisture in the soil during mixing with the soil was observed by actually mixing with the soil and dispersing the resin.

(6) Plant growth test As a plant growth test, a seedling growth test using cucumber and a growth test using geranium seedlings transplanted were performed. The result of the cucumber seedling raising test was determined by the degree of leaf withering or the growth index observed 25 days after growth.

The growth index was calculated as follows. First, take out the grown plants together with their roots, wash them with water to remove mud, etc., absorb excess water with a paper towel, divide them into above ground and below ground, or into leaves and roots.
/ Book) was measured. Then, it was air-dried and the air-dry weight (g / piece) per one piece was calculated. The ratio of the fresh weight and the air dry weight when the test material is used with respect to the fresh weight and the air dry weight of the plant in the standard plot grown under the same growth conditions except that the test material is not used, as 100. It was expressed by.

In the growth test using geranium seedlings, geranium seedlings were transplanted using soil contaminated with seedling blight, a 60-day growth test was performed, and the control rate of seedling blight was calculated. did. In addition, this control group was used by irrigating 50 ml of a 1000-fold diluted solution of Tachigaren wettable powder (manufactured by Sankyo Co., Ltd.) per strain.

<Production Example 1 of Crosslinked Polyaspartic Acid> 7.2 parts of lysine methyl ester dihydrochloride and 22.6 parts of lysine monohydrochloride were dissolved in 40 parts of distilled water, and caustic soda.
Eight parts were added little by little to neutralize to prepare an aqueous lysine solution. On the other hand, 100 parts of a polysuccinimide having a weight average molecular weight of 96,000 was added to dimethylformamide (DM
F) Dissolved in 400 parts, added the lysine aqueous solution, stirred for 1 hour at room temperature, stopped stirring, and reacted for 20 hours. The reaction product was transferred to a mixer equipped with a blade with stirring blades, and 400 parts of distilled water and 400 parts of methanol were added.
The gel was chopped for 5 minutes, and 129.7 parts of a 27% by weight aqueous sodium hydroxide solution was further added dropwise over 2 hours. After dripping,
Stir for an additional 2 hours and then p
Neutralized until H = 7. After the neutralization, 300 parts of methanol was further added, and the precipitate was dried at 60 ° C. and pulverized using a sample mill to obtain 143 parts of a crosslinked polyaspartic acid (water-absorbing polymer). When the biodegradability was examined, the biodegradability was as good as 102%.

<Production Example 2 of Crosslinked Polyaspartic Acid> 100 parts of polysuccinimide having a weight-average molecular weight of 96,000 was dissolved in 400 parts of DMF, and a solution of 3.59 parts of hexanediamine in 20 parts of DMF was added. For 1 hour, stop stirring, and react for 20 hours. The obtained reaction product was treated in the same manner as in Production Example 1 to obtain a crosslinked polyaspartic acid. When the biodegradability was examined, the biodegradation rate was 10
It was as good as 3%.

<Comparative Production Example 1 of Other Resins>
A crosslinked polyacrylic acid was obtained according to the method described in Japanese Patent No. 30710. The water absorption of this resin in tap water is 27
Although it was as good as 0-fold, the biodegradability was 2.2%, indicating no biodegradability.

Example 1 The crosslinked polyaspartic acid obtained in Production Example 1 was pulverized and subjected to a mesh pass to give a particle size of 105.
Particles of μm to 500 μm were obtained. Then, the particles 10
Parts: 50 parts of methanol and 0.5 parts of sorbitan monolaurate (trade name: Reodol SP-L10, Kao Corporation)
Was added to the dissolved solution and mixed. Thereafter, methanol was distilled off under reduced pressure to obtain core-shell particles having a shell phase containing sorbitan monolaurate.

Example 2 The same treatment as in Example 1 was carried out except that oleic acid monoglyceride (trade name: Reodol MO-60, manufactured by Kao Corporation) was used instead of sorbitan monolaurate. Core-shell particles having a shell phase containing acid monoglyceride were obtained.

Example 3 The procedure of Example 1 was repeated except that polyoxyethylene (26) sorbitan monooleate (trade name: Reodol TW-0120, manufactured by Kao Corporation) was used instead of sorbitan monolaurate. Similarly, core-shell particles having a shell phase containing polyoxyethylene (26) sorbitan monooleate were obtained.

Example 4 Lauryl trimethyl ammonium chloride was produced in the same manner as in Example 1 except that lauryl trimethyl ammonium chloride (trade name: Cotamine 24P, manufactured by Kao Corporation) was used instead of sorbitan monolaurate. A core-shell particle having a shell phase containing was obtained.

Example 5 Core-shell particles having a shell phase containing sodium octanesulfonate were obtained in the same manner as in Example 1 except that sodium octanesulfonate was used instead of sorbitan monolaurate.

Example 6 Instead of sorbitan monolaurate, polyvinylpyrrolidone (weight average molecular weight 63
Core shell particles having a shell phase containing polyvinylpyrrolidone were obtained in the same manner as in Example 1 except that (1) was used.

Comparative Example 1 The crosslinked polyaspartic acid obtained in Production Example 1 was pulverized in the same manner as in Example 1 and mesh-passed to obtain core particles having a particle size of 105 to 500 μm. This core particle was used for evaluation as it was.

<Evaluation of Examples 1 to 6 and Comparative Example 1> With respect to each of the particles obtained in Examples 1 to 6 and Comparative Example 1, the measurement of the water absorption rate and the production test of “Mamako” were performed. The results are shown in Table 1 below.
Shown in

[0128]

[Table 1] Example 7 The crosslinked polyaspartic acid obtained in Production Example 1 was pulverized and passed through a mesh to obtain core particles having a particle size of 0.5 to 1.5 mm. The core particles are immersed in a 40% by weight polysuccinimide DMF solution, pulled up from the solution, and dried at 120 ° C. for 20 hours under reduced pressure of 60 mmHg to remove the solvent, thereby coating with a polysuccinimide. Particles were obtained. The particles had a moisture absorption of 22.9% after 20 hours, and did not adhere for more than 20 hours in the stickiness test.

As cultivation soil, 1700 parts of Super Soil No. 2 (horticultural floor soil) and 5.1 parts of particles coated with the above-mentioned polysuccinimide were mixed. At this time, non-uniformity such as a lump of the resin due to stickiness of the resin was not observed. 210 parts of this mixture was placed in a 500 ml plastic pot, and a growth test was carried out using cucumber as a test crop.

[0130] Regarding watering, first, sufficient watering was performed until saturation was reached, and then a growth test was performed for 10 days without watering. In addition, the test is conducted up to 25 days,
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 5, and the average of 5 times was calculated. As a standard plot, 80 parts of water was irrigated four times by 10 days after transplantation without addition of a water retention agent, and then sufficient standard irrigation was performed every day until 25 days.

As a result, after 25 days, the main stem length was 13.5.
cm, stem dry weight is 0.30 parts / tree, growth index is 12
8. The leaf dry weight is 0.77 parts / book, and the growth index is 139.
The root dry weight is 0.1290 parts / book, the growth index is 160,
The dry weight of foliage was 1.16 parts / row, and the growth index was 148, indicating remarkable growth promotion.

Example 8 The crosslinked polyaspartic acid obtained in Production Example 2 was pulverized and subjected to a mesh pass to obtain a particle size of 0.5.
~ 1.5 mm core particles were obtained. The core particles are immersed in a chloroform solution of polylactic acid having a concentration of 10% by weight, pulled up from the solution, dried at 60 ° C. for 5 hours, and the immersion drying operation is repeated three times to obtain particles coated with polylactic acid. I got The moisture absorption of these particles was 16.3 after 20 hours.
% And did not adhere for more than 20 hours in the stickiness test.

0.6 parts of the particles (granules) coated with the polylactic acid were added to Super Soil No. 2 (horticultural floor soil) 200
The resulting mixture was mixed well to obtain a soil composition. This soil composition was subjected to a plant growth test using cucumber in the same manner as in Example 7 under the condition of limiting the number of times of watering. As a result, after 25 days, the main stem length was 13.9 cm and the stem dry weight was 0.3 cm.
The growth index is 148 and the dry weight of leaf is 0.84 at 34 parts / tree.
Parts / book, growth index: 152, root dry weight: 0.1405
Per part / row, the growth index was 174, the dry weight of foliage was 1.18 parts / row, and the growth index was 151, indicating remarkable growth promotion.

Example 9 Particles coated with ethyl cellulose were obtained in the same manner as in Example 8, except that ethyl cellulose was used instead of polylactic acid. The particles had a moisture absorption of 17.7% after 20 hours, and did not adhere for more than 20 hours in the stickiness test.

[0135] 0.6 parts of the particles (granules) coated with the ethylcellulose were mixed with Super Soil No. 2 (horticultural floor soil).
By mixing well with 200 parts, a soil composition was obtained. This soil composition was subjected to a plant growth test using cucumber in the same manner as in Example 7 under the condition of limiting the number of times of watering. As a result, as a result, after 25 days, the main stem length was 13.
7cm, stem dry weight 0.32 parts / book, growth index 13
8. The leaf dry weight is 0.78 parts / book, the growth index is 142,
Root dry weight is 0.1373 parts / book, growth index is 170,
The dry weight of foliage was 1.17 parts / row, and the growth index was 150, indicating remarkable growth promotion.

<Example 10> 98 parts of the crosslinked polyaspartic acid obtained in Production Example 1, tatigalen wettable powder (Sankyo Co., Ltd.)
2 parts) was placed in a mixer and mixed until uniform.
0.42 parts of this mixture was placed in a tableting machine (Model 7A-SM manufactured by Kikusui Seisakusho) with a die having a diameter of 10 mm, and the tablets were adjusted by adjusting the upper punch so that the thickness of the tablets would be 4 mm. A disk-shaped tablet with corners was obtained. The tablet was placed in FL-80 manufactured by Freund Corporation and hydroxypropylcellulose 2
% Ethanol solution was sprayed to obtain particles coated with hydroxypropylcellulose. The moisture absorption of the particles was 3.9% after 20 hours, and did not adhere for more than 20 hours in the stickiness test.

Soil contaminated with seedling damping was collected, geranium seedlings were transplanted, holes having a depth of 3 to 5 cm were made around the plant, and particles coated with hydroxypropyl cellulose were introduced. A growth test was performed in standard irrigation for 60 days. The control rate of seedling blight is almost 100%,
No root rot was observed.

Example 11 In the same manner as in Example 8, particles coated with polylactic acid were obtained. A tablet was obtained in the same manner as in Example 10, except that 300 parts of the particles and 6 parts of Tachigaren wettable powder (manufactured by Sankyo Co., Ltd.) were mixed and used. This tablet and 100 parts of powdered polylactic acid (trade name LACEA, manufactured by Mitsui Chemicals, Inc.) are mixed at a resin temperature of 180 to 190 ° C., and the tablet is pulled up and cooled to obtain particles having a shell phase containing polylactic acid. I got The moisture absorption of the particles was 15.9% after 20 hours, and was 2% in the stickiness test.
It did not adhere for more than 0 hours. A geranium growth test was carried out in the same manner as in Example 10. As a result, the control rate of seedling blight was almost 100%, and neither chemical damage nor root rot was observed.

<Comparative Example 2> With respect to the particles of the crosslinked polyacrylic acid obtained in Comparative Production Example 1, a growth test was carried out in the same manner as in Example 7 while limiting the number of times of watering of cucumber. As a result, when the resin and the soil were mixed, the resin became sticky due to the stickiness of the resin and was not uniformly dispersed. Also, as a result of the plant growth test, after 25 days, the main stem length was 12.7 cm, the stem dry weight was 0.17 parts / row, the growth index was 80, the leaf dry weight was 0.47 parts / row, Index is 85, root dry weight is 0.07
The growth index was 91, the dry weight of foliage was 0.71 parts / row, and the growth index was 91 at 4 parts / row, indicating a growth inhibition.

<Comparative Example 3> The crosslinked polyaspartic acid obtained in Production Example 1 was pulverized and subjected to a mesh pass to obtain a particle size of 0.5.
~ 1.5 mm particles were obtained. The moisture absorption of these particles was 25.5% after 20 hours, and adhered within 10 minutes as a result of the stickiness test. For these particles, a growth test was carried out in the same manner as in Example 7 while limiting the number of times of cucumber irrigation. As a result, after 25 days, the main stem length was 13.4 cm, the stem dry weight was 0.30 parts / tree, the growth index was 128, and the leaf dry weight was 0.7.
8 copies / line, growth index 141, root dry weight 0.127
4 parts / row, growth index: 158, foliage dry weight: 1.16
Per part / row, the growth index was 148, which was good. But,
When the resin and the soil were mixed, the resin became sticky due to the stickiness of the resin and was not uniformly dispersed.

<Comparative Example 4> The procedure was carried out except that 50 ml of a 1000-fold diluted solution of Tatigalen wettable powder (manufactured by Sankyo Co., Ltd.) was used per i.p. without using the particles coated with hydroxypropyl cellulose. A geranium growth test was performed in the same manner as in Example 10. As a result, 60
Within days, root rot was observed in 30% of the seedlings.

<Comparative Example 5> A geranium growth test was carried out in the same manner as in Example 10, except that the particles of the crosslinked polyacrylic acid obtained in Comparative Production Example 1 were used. As a result, root rot was observed in 40% of the seedlings 60 days after transplantation.

[0143]

As described above, according to the present invention,
It is possible to provide crosslinked polyamino acid-containing particles having no water accumulation property after use, a high water absorption rate, no stickiness due to moisture absorption or soil moisture, and excellent water retention ability and sustained release of active ingredients. Specifically, for example,
To play. . There is no problem with conventional crosslinked polyamino acid-containing particles that "mamako" is formed upon contact with water and the water absorption rate is significantly reduced. That is, no "mamako" is generated, the dispersibility in water is excellent, and the water absorption rate is excellent. . There is no stickiness of the surface due to moisture and the like, and the operability is remarkably excellent. . Difficult to adsorb moisture and water vapor, and remarkably low in hygroscopicity. . After use, it does not accumulate in soil and has excellent water retention. . Useful for sustained release of active ingredients. . It is useful in the use of a soil conditioner for promoting plant growth.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 101/16 C08L 101/14 101/14 C09K 17/32 H C09K 17/32 17/50 H 17/50 C08L 101 / 00A // C09K 101: 00 (72) Inventor Toshio Kato 580-32 Takuji Nagaura, Sodegaura-shi, Chiba Inside Mitsui Chemicals, Inc. (72) Hiroaki Tamaya 580 Takuji Nagaura, Sodegaura-shi, Chiba 580 No. 32 Mitsui Chemicals Co., Ltd. (72) Inventor Akio Fukuoka 11-8 Nihonbashi Odenmacho, Chuo-ku, Tokyo Inside Mitsui Toatsu Fertilizer Co., Ltd.

Claims (23)

[Claims] 1. A core / shell structure in which at least a part of a surface of a core phase is covered with at least one shell phase, wherein the core phase is composed of at least crosslinked polyamino acid-containing particles, and the shell phase is a coating material. And a crosslinked polyamino acid-containing particle. 2. A core / shell structure in which at least a part of the surface of a core phase is covered with at least one shell phase, wherein the core phase is composed of at least crosslinked polyamino acid-containing particles, and the shell phase comprises a resin. A crosslinked polyamino acid-containing particle which is constituted by containing. 3. The crosslinked polyamino acid-containing particles according to claim 1, wherein the crosslinked polyamino acid includes a crosslinked acidic polyamino acid. 4. The crosslinked polyamino acid-containing particles according to claim 3, wherein the crosslinked acidic polyamino acid contains a crosslinked polyaspartic acid. 5. The crosslinked polyamino acid-containing particles according to claim 1, wherein the coating material contains a surfactant. 6. The resin according to claim 2, wherein the resin contains a biodegradable polymer.
5. The crosslinked polyamino acid-containing particles according to any one of items 4 to 4. 7. The crosslinked polyamino acid-containing particles according to claim 6, wherein the biodegradable polymer contains an aliphatic polyester. 8. The crosslinked polyamino acid-containing particles according to claim 7, wherein the aliphatic polyester contains (co) polyhydroxycarboxylic acid. 9. The (co) polyhydroxycarboxylic acid is
9. The crosslinked polyamino acid-containing particles according to claim 8, comprising (co) polylactic acid. 10. The crosslinked polyamino acid-containing particles according to claim 6, wherein the biodegradable polymer contains polysuccinimide. 11. A method for producing the crosslinked polyamino acid-containing particles according to claim 1, wherein the surface of the crosslinked polyamino acid-containing particles is coated with a coating material solution or a coating material in a molten state. A method for producing crosslinked polyamino acid-containing particles, comprising a step of forming at least one shell phase in at least a part of the above. 12. A method for producing the crosslinked polyamino acid-containing particles according to claim 2, wherein a resin solution or a resin in a molten state is applied to the surface of the crosslinked polyamino acid-containing particles, so that at least the surface of the crosslinked polyamino acid-containing particles is coated. A method for producing crosslinked polyamino acid-containing particles, the method comprising partially forming at least one shell phase. 13. The method for producing crosslinked polyamino acid-containing particles according to claim 11, wherein the crosslinked polyamino acid includes a crosslinked acidic polyamino acid. 14. The method for producing crosslinked polyamino acid-containing particles according to claim 13, wherein the crosslinked acidic polyamino acid contains crosslinked polyaspartic acid. 15. The method for producing crosslinked polyamino acid-containing particles according to claim 11, 13, or 14, wherein the coating material contains a surfactant. 16. The method for producing crosslinked polyamino acid-containing particles according to claim 12, wherein the resin contains a biodegradable polymer. 17. The method for producing crosslinked polyamino acid-containing particles according to claim 16, wherein the biodegradable polymer contains an aliphatic polyester. 18. The method for producing crosslinked polyamino acid-containing particles according to claim 17, wherein the aliphatic polyester contains (co) polyhydroxycarboxylic acid. 19. The (co) polyhydroxycarboxylic acid is
The method for producing crosslinked polyamino acid-containing particles according to claim 18, which comprises (co) polylactic acid. 20. The method according to claim 16, wherein the biodegradable polymer contains polysuccinimide. 21. Crosslinked polyamino acid-containing particles obtained by the method according to any one of claims 11 to 20. A sanitary material comprising the crosslinked polyamino acid-containing particles according to any one of claims 1 to 10 or 21. 23. A soil conditioner comprising the crosslinked polyamino acid-containing particles according to any one of claims 1 to 10 or 21.