JP2006117918A - Sustained-release agent for functional water-soluble material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a sustained-release agent for a functional water-soluble material which can prevent a functional water-soluble material from being discharged early by having sufficient strength to resist to water flows and agitation and by securing a sufficient carrying amount of the functional water-soluble material. <P>SOLUTION: The sustained-release agent for the water-soluble material comprising a water-insoluble resin, a structural material, and the functional water-soluble material, consisting of a resin composition in which these materials are mutually distributed are manufactured wherein the content ratio of the functional water-soluble material in the resin composition is 20-90 wt.%, and at least either one of the structural material or the water-insoluble resin is hydrophilic. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a functional water-soluble substance sustained-release material that stably releases a functional water-soluble substance into water.

  Conventionally, there are granulated products such as fertilizers as sustained release materials that release functional water-soluble substances. However, since such a granulated product itself has a property of collapsing, stable and sustained release could not be performed in a state of being stirred or exposed to a water stream.

  Further, there is a sustained release material in which the release of the functional water-soluble substance is controlled by kneading the functional water-soluble substance with wax or the like. However, when the ratio of the wax or the like is high, the sustained-release material has an extremely slow release of the functional water-soluble substance, or the function in the inside even if the functional water-soluble substance near the surface is released. In some cases, the release of the water-soluble water-soluble substance is stopped without being released. On the other hand, if the ratio of the functional water-soluble substance is high, the functional water-soluble substance may be released quickly, or the particle strength may be low and the water flow or stirring may not be sustained. May cause problems.

  On the other hand, Patent Document 1 discloses that the hydrophilic porous body and the above are embedded by embedding a functional water-soluble substance and a hydrophobic substance in the pores of the hydrophilic porous body having high strength. A sustained-release functional agent is described in which the functional water-soluble substance is gradually released through a gap formed between the hydrophobic substance and the hydrophobic substance.

Japanese Patent Laid-Open No. 10-17846

  However, the sustained-release functional agent described in Patent Document 1 has a large gap between the hydrophilic porous body and the hydrophobic substance because the entire hydrophilic porous body expands due to water permeation. In some cases, the release of soluble water-soluble substances was accelerated. Moreover, since the volume which a hydrophilic porous body occupies is large, the load of the functional water-soluble substance has decreased.

  Therefore, the present invention has a strength that can withstand water flow and agitation, secures an amount of the functional water-soluble substance, and suppresses the release of the functional water-soluble substance at an early stage. The purpose is to obtain a release material.

  The present invention includes a water-insoluble resin, a structural material, and a functional water-soluble substance and is composed of a resin composition in which these are dispersed with each other, and the content ratio of the functional water-soluble substance in the resin composition is 20 to 20%. The above-mentioned problem is solved by a functional water-soluble substance sustained-release material that is 90% by weight and at least one of the structural material and the water-insoluble resin is hydrophilic.

  Since the functional water-soluble substance sustained-release material according to the present invention is held in the water-insoluble resin, rapid release of the functional water-soluble substance can be suppressed. In addition, since the structural material is dispersed in the water-insoluble resin and at least one of the structural material and the water-insoluble resin is hydrophilic, a path through which the functional water-soluble substance is gradually released can be formed inside the material. It is possible to prevent the sexual substance from remaining. Furthermore, release can also be suppressed more gently by coating the whole with resin.

  Further, unlike the hydrophilic porous body, water does not penetrate at once but gradually penetrates, so that the functional water-soluble substance is gradually released along with the penetration. In addition, it is possible to use a structural material and a water-insoluble resin rather than using a hydrophilic porous body, so that the volume occupied by other than the functional water-soluble substance can be reduced. The amount of water soluble substance can be increased.

Hereinafter, the present invention will be described in detail.
The present invention is a functional water-soluble substance sustained-release material composed of a resin composition containing a water-insoluble resin, a structural material, and a functional water-soluble substance.

  The functional water-soluble substance refers to a substance that dissolves in water and exhibits some function. For example, chemical fertilizers include potassium chloride, lime superphosphate, ammonium sulfate, potassium sulfate, etc. , Iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, cyclohexanediaminetetraacetic acid, and the like. Examples of the flocculant include polyaluminum chloride, potassium alum, and vanadium sulfate, and examples of the surfactant include alkylbenzenesulfonic acid. , Polyoxyethylene alkyl ether, and the like, and antibacterial agents include copper bromide, copper chromate, silver nitrate, aluminum sulfate, iodine, copper hydroxide, copper sulfate, and the like. No., New Coxin, Phloxin, Acid Red, etc. Examples include resorbic acid, sodium erythorbate, kojic acid, ascorbic acid, sodium ascorbate and the like. Examples of medium components include citric acid, gluconic acid, peptone, sodium nitrate, sodium phosphate, and vitamins include thiamine. , Ascorbic acid, nicotinic acid and the like, amino acids include glutamic acid, alanine, aspartic acid, glycine, lysine hydrochloride and the like, and insecticides include acephate, anabasine, cartap, trichlorfone and the like, Examples of bactericides include kasugamycin, oxycarboxin, and validamycin A, herbicides include amitrol, sulfamate, die coat, trichloroacetic acid, and the like, and growth regulators include Ecephone and N (dimethylamino). Sukushinamin acid, chlormequat, and examples of the functional water-soluble substance other do not belong to the above categories, humectants, freshness-keeping agents, rust inhibitors, slime control agents, pH adjusting agents and the like. These substances may be used for applications other than the functions described above. For example, ascorbic acid or ascorbate such as sodium ascorbate may be used mainly to remove free residual chlorine contained in tap water. Good. A plurality of these substances may be used in combination. However, in that case, it is necessary that the substances used in combination do not lose their effects by reacting with each other. The functional water-soluble substance sustained-release material according to the present invention is a sustained-release material that gradually releases these functional water-soluble substances to exert their effects.

  The water-insoluble resin is a resin that molds the structural material and the functional water-soluble substance while suppressing the rapid release of the functional water-soluble substance and needs to be solid at room temperature when used. is there. Examples of the water-insoluble resin include a resin that is heated and melted to be cooled and solidified, a resin that is reacted and solidified in a liquid state at the time of molding, and a resin that is solidified by evaporating the solvent after being dissolved or dispersed in water or an organic solvent at the time of molding. In order to prevent the functional water-soluble substance from being altered when mixed with the functional water-soluble substance, the reactivity with the functional water-soluble substance needs to be low.

  Examples of the water-insoluble resin that is heated and melted to cool and solidify include rosin resins, waxes, higher fatty acids, higher alcohols, sugar esters and the like as hydrophobic water-insoluble resins. Among these, as the rosin resin, (1) normal rosin includes gum rosin, wood rosin, tall oil rosin and the like, and (2) modified rosin includes hydrogenated rosin, disproportionated rosin and polymerized rosin. (3) Examples of the rosin ester include rosin methyl ester and hydrogenated rosin glycerin ester. Examples of the wax include (1) animal waxes such as beeswax, beef wax, and lanolin, (2) plant waxes such as wood wax, rice wax, and carnauba wax, and (3) mineral waxes. (4) Petroleum wax includes paraffin wax, microcrystalline wax, and the like. Examples of the higher fatty acid include myristic acid, palmitic acid, stearic acid, behenic acid and the like. Examples of the higher alcohol include stearyl alcohol. Examples of the sugar ester include sucrose stearate ester, sucrose palmitate ester, and sucrose oleate ester. Examples of the hydrophilic water-insoluble resin include vinyl acetate resin.

  Next, examples of the water-insoluble resin that reacts and solidifies with a liquid at the time of molding include a urethane resin, an epoxy resin, an ultraviolet curable resin, an electron beam curable resin, and the like as the hydrophobic water-insoluble resin. Examples of hydrophilic water-insoluble resins include crosslinked polyvinyl alcohol and water insolubilized materials such as polyvinyl acetal.

  Furthermore, as an example of a water-insoluble resin that is dissolved or dispersed in water or an organic solvent at the time of molding and then solidifies by evaporation of the solvent, first, as a hydrophobic water-insoluble resin, vinyl acetate resin, acrylic resin, etc. Is mentioned. In addition, water-insoluble resins obtained by introducing an ionic group into a hydrophobic resin and making it hydrophilic, such as water-based emulsions such as urethane resins and acrylic resins, can be mentioned.

  The structural material is a material that can be dispersed in the water-insoluble resin or the functional water-soluble substance and increases the strength of the functional water-soluble substance sustained-release material, such as pulp fiber, cellulose fiber, etc. Examples include hydrophilic fibers, hydrophobic fibers such as polyethylene fibers and polyester fibers, and hydrophilic viscous minerals that can retain water between layers.

  Further, at least one of the structural material and the water-insoluble resin needs to be hydrophilic. This makes it possible to impart the necessary hydrophilicity to the component that is composed of the water-insoluble resin and the structural material and retains the functional water-soluble substance. Even if the water-insoluble resin is hydrophobic, if the structural material is hydrophilic, water and the functional water-soluble substance can move through the structural material as a route, and the functional water-soluble substance is released. can do. Conversely, even if the structural material is hydrophobic, the functional water-soluble substance can be released through the water-insoluble resin if the water-insoluble resin is hydrophilic. Note that both the water-insoluble resin and the structural material may be hydrophilic.

  In order to have the hydrophilicity necessary for the above-described component that retains the functional water-soluble substance, specifically, depending on the water absorption amount of the molded product of the water-insoluble resin and the structural material produced without the functional water-soluble substance. The water absorption amount per 1 g of the molded product is preferably 0.1 to 2 g.

  In order to produce the functional water-soluble substance sustained-release material according to the present invention, first, the resin composition in which the water-insoluble resin, the structural material and the functional water-soluble substance are mixed and these substances are dispersed with each other. And In addition to the water-insoluble resin, the structural material, and the functional water-soluble substance, there may be one contained.

  Of the functional water-soluble substance sustained-release material according to the present invention, the content of the functional water-soluble substance in the resin composition needs to be 20 to 90% by weight, and is 30 to 90% by weight. And preferred. If the content of the functional water-soluble substance is less than 20% by weight, the amount of the functional water-soluble substance is so small that the release of the functional water-soluble substance ends quickly, and the function as a sustained-release material becomes insufficient. End up. On the other hand, if it exceeds 90% by weight, the water-insoluble resin and the structural material that support the material become insufficient, so that it is difficult to mold, or even if it can be molded, it may collapse and be unable to be released slowly. .

  The content of the water-insoluble resin in the resin composition is preferably 5 to 70% by weight, and the content of the structural material is preferably 5 to 50% by weight. When mixed at such a ratio, the functional water-soluble substance can be gradually released with the strength to withstand water flow and stirring.

  As a method of molding this resin composition, there is a method of granulating. Examples of the granulation method include rolling granulation, extrusion granulation, compression granulation, and stirring granulation. Specific examples thereof include a method of intermittently extruding, cutting and cooling the resin composition heated and melted into a granular material when using a water-insoluble resin that is melted by heating and solidifying by cooling. It is done. In addition, when a water-insoluble resin that is dissolved or dispersed in water or an organic solvent at the time of molding and is subsequently solidified by evaporating the solvent is used, there is a method of extrusion granulation and drying to form a granular material. Can be mentioned. Furthermore, the method of compressing the said resin composition, tableting, and making it a granular material is mentioned. Although the shape of the granular material obtained by granulation like these is not specifically limited, Spherical shape, cylindrical shape, triangular prism shape, etc. are mentioned. In addition, in order to obtain a spherical granular material, a method of tableting directly into a spherical shape, or after obtaining the granular material having a corner or a bulge, a spherical particle sizer is used to roll the particles. The method of performing a process etc. are mentioned.

  As an apparatus for performing the granulation as described above, for example, a resin composition supplied between a disk having a large number of holes with a diameter of about several millimeters and a roller is compressed and molded by rotation of the roller to form a cylindrical shape. A disk pelleter to be used as a pellet, or a plate having a plurality of recesses provided with a lower punch that can be pushed up at the bottom. After the resin composition is supplied to these recesses and pressed from above with an upper punch, the resin composition is recessed. And a tableting machine such as a rotary tableting machine that takes out the tablet-like granular material by pushing up from the bottom of the tablet, and a Malmerizer (spherical granulator) that spherically regulates the obtained non-spherical granular material. Moreover, as an apparatus which extrudes the said heat-melted resin composition, the dispenser which discharges a resin composition quantitatively is mentioned, There exists the method of cut | disconnecting and granulating what was extruded intermittently by this.

  Since this functional water-soluble substance sustained-release material ensures strength by the structural material and the water-insoluble resin, it is difficult to break even if it is provided in a place where it is exposed to a water stream or stirred. Sustained release. For example, the functional water-soluble substance sustained-release material using ascorbic acid or ascorbate as the functional water-soluble substance is attached to a water outlet such as a tap or a shower head, thereby providing a sustained release. Ascorbic acid thus produced makes it possible to remove free residual chlorine contained in tap water.

  The granulated product obtained by the above granulation may be used as it is as a functional water-soluble substance sustained-release material according to the present invention, or the surface of the granulated product is a resin such as shellac or the above water-insoluble resin. It may be used as a functional water-soluble substance sustained-release material that has been coated with, and further reduces the release amount of the functional water-soluble substance. For example, when both the water-insoluble resin and the structural material are hydrophilic, when the release amount of the functional water-soluble substance is large, the release amount is adjusted to maintain the effect longer. Can be made of wood. The resin to be coated may be the same as or different from the water-insoluble resin. Further, when the resin is hydrophobic, the effect of lowering the release amount obtained by coating is higher. Examples of the coating method include pan coating, rolling coating, and fluid coating using a resin melted by heating or a resin dissolved or dispersed in water or an organic solvent. Examples of the apparatus used for this coating include sugar coating machines that perform pan coating.

  The functional water-soluble substance sustained release material according to the present invention can exhibit the effect of the functional water-soluble substance over a long period of time by releasing the functional water-soluble substance. For example, when ascorbic acid is used as the functional water-soluble substance, the functional water-soluble substance sustained-release material according to the present invention is used to remove free residual chlorine mainly contained in tap water over a long period of time. it can.

  Hereinafter, the present invention will be described more specifically with reference to examples. First, the raw materials used and the test / measurement method will be described.

・ Functional water-soluble substances: Ascorbic acid (manufactured by Nacalai Tesque)
・ Functional water-soluble substances: Food Blue No. 1 (manufactured by Daikoku Dye)
・ Functional water-soluble substances: ethylenediaminetetraacetic acid (manufactured by Nacalai Tesque)
Water-insoluble resin (hydrophobic): Paraffin wax (Nippon Seiwa Co., Ltd .: HNP-9, indicated as “wax” in the table)
Water-insoluble resin (hydrophobic): polyester-based UV curable resin (Arakawa Chemical Industries, Ltd .: Beam set 750, indicated as “UV” in the table)
Water-insoluble resin (hydrophobic): Urethane resin aqueous emulsion (Dainippon Ink & Chemicals, Inc .: Hydran HW930, indicated as “urethane” in the table)
Water-insoluble resin (hydrophilic): polyvinyl alcohol (manufactured by Kuraray Co., Ltd .: PVA124, hereinafter referred to as “PVA”)
・ PVA crosslinking agent: (Sumitomo Chemical Co., Ltd .: Sumire's Resin 675A)
Structural material (hydrophilic fiber): pulp fiber (manufactured by Nippon Paper Chemicals Co., Ltd .: KC Flock W-200, indicated as “pulp” in the table)
Structural material (hydrophobic fiber): polyethylene fiber (Daiwabo Co., Ltd .: Daiwabo NBF, indicated as “PE” in the table)
・ Coating resin: Shellac (Gifu Shellac Manufacturing Co., Ltd .: GSN)
-Porous material: Cellulose beads (manufactured by Rengo Co., Ltd .: AH-4050L)

(Granular strength test)
300 mL of water was put into a 1 L beaker, and 30 g of the granular material obtained in each Example and Comparative Example was added thereto. This was stirred with a stirring blade at 100 rpm for 1 hour, and the change in appearance was observed.

(Water absorption of molded products of water-insoluble resin and structural material)
Of the composition of the molded product produced in each example, a molded product composed only of a water-insoluble resin and a structural material, which does not contain a functional water-soluble substance, is produced and immersed in water for 1 hour. The amount of water absorption per gram of the molded product was measured.

(Measurement of dissolution rate of ascorbic acid)
30 g of the granular material obtained in each of the examples and comparative examples was put in a net and mounted in a pipe having a diameter of 4 cm, and tap water was allowed to flow through the pipe at a flow rate of 8 L / min. Ascorbine that was initially contained was taken out of the granular material whose accumulated water flow was 1000L, 2000L, 4000L (measured at 8000L and 16000L in Examples 4 to 10), dried, and measured for its weight loss. It was calculated as the dissolution rate relative to the amount of acid.

(Example 1, Comparative Examples 1-3)
Paraffin wax, which is a water-insoluble resin, is added to a Henschel mixer (Mitsui Mining Co., Ltd .: FM20) and melted at 90 ° C. Or PE) is added and mixed at the ratio shown in Table 1, and this is dispensed on a cooled steel plate using a dispenser (Musashi Engineering Co., Ltd .: ML-505X) equipped with a discharge nozzle with a hole diameter of 3 mm. The product was extruded intermittently from a nozzle and cut to obtain granules having a particle size of about 4 mm. In Comparative Example 1, no structural material is contained, in Comparative Example 2, both the water-insoluble resin and the structural material are hydrophobic, and in Comparative Example 3, the content of ascorbic acid exceeds 90% by weight. .

(Comparative Example 4)
Paraffin wax was added to a Henschel mixer (manufactured by Mitsui Mining Co., Ltd .: FM20), melted at 90 ° C., and mixed with ascorbic acid in the proportions shown in Table 1 and embedded in the pores of cellulose beads. About 4 mm granular material was obtained.

(Result 1)
When a strength test was performed on these granular materials, the granular materials according to Comparative Example 3 were disintegrated, and the other granular materials were not changed in appearance. Moreover, about each example, Table 1 shows the water absorption of what was molded without adding a functional water-soluble substance. Furthermore, the calculated dissolution rate is shown in Table 1. In Comparative Example 1 composed of only a water-insoluble resin without using a structural material, and Comparative Example 2 in which both the structural material and the water-insoluble resin are hydrophobic, the release of ascorbic acid was not completed, and the inside of the material Remained. Further, in Comparative Example 3 in which the proportion of ascorbic acid was large and the proportion of the water-insoluble resin and the structural material was small, the release was completed quickly and the release was not sustained. In Comparative Example 4, the content of the functional water-soluble substance was small, and the water penetration into the cellulose beads was fast, so that the release of the functional water-soluble substance was completed quickly.

(Examples 2 and 3)
Instead of ascorbic acid of Example 1, food blue 1 (Example 2) and ethylenediaminetetraacetic acid (Example 3) were used as the functional water-soluble substance in the same procedure as Example 1, The granular material containing these was obtained, respectively. Table 2 shows the results of measuring the dissolution rate of these granular materials. Both food blue 1 and ethylenediaminetetraacetic acid, which have lower water solubility than ascorbic acid, had lower elution rates than ascorbic acid.

Example 4
A water-dispersible urethane resin water-based emulsion that is a water-insoluble resin, ascorbic acid that is a functional water-soluble substance, and pulp fibers that are a structural material in the proportions shown in Table 3 at a high speed stirring granulator ((stock ) Dalton: SPG-25) added and mixed to obtain a resin composition, which was put into a disk pelleter (Dalton Co., Ltd .: F-5) to form a pellet, and then a Malmerizer (( Spherical sizing was performed using Dalton Co., Ltd. (Q-400). Here, the high-speed stirring granulator does not perform granulation but is used for kneading. This was dried with a vibration dryer (manufactured by Dalton Co., Ltd .: MDV-1200) set at 100 degrees to obtain a granular material having a particle size of about 4 mm.

(Example 5)
An ultraviolet curable resin, which is a water-insoluble resin, ascorbic acid, which is a functional water-soluble substance, and pulp fibers, which are structural materials, are added and mixed in the proportions shown in Table 3 using the same apparatus as in Example 4, and extruded. After the granule and spherical sizing, the resin was cured by ultraviolet irradiation (manufactured by Eiko Co., Ltd .: 300 W high pressure mercury lamp) to obtain a granular material having a particle size of about 4 mm.

(Example 6)
As a water-insoluble resin, an aqueous solution in which PVA and its cross-linking agent are mixed at a weight mixing ratio of 10: 1, ascorbic acid as a functional water-soluble substance, and polyethylene fiber as a structural material are added at a ratio shown in Table 3. Then, by the same procedure as in Example 4, a granular material having a particle size of about 4 mm was obtained.

(Example 7)
The granular material obtained in Example 4 was surface-coated with an ethanol solution containing 20% by weight of shellac using a sugar coating machine (manufactured by Hata Iron Works Co., Ltd .: HC-200 type), and then the ethanol was evaporated. The granular material which is the weight ratio of Table 3 was obtained.

(Example 8)
The granular material obtained in Example 4 was surface-coated with a urethane resin aqueous emulsion using a sugar coating machine (manufactured by Hata Iron Works, Inc .: HC-200 type), and then water was evaporated. Granules having a weight ratio were obtained.

(Result 2)
When the strength test was conducted, none of these granular materials remained unchanged in shape. Moreover, when the elution rate was calculated, it was as shown in Table 3, and ascorbic acid could be gradually released in all cases. In particular, Example 7 was able to gradually release ascorbic acid for a longer time than Example 4 that was not coated. Furthermore, for each example, the water absorption of those molded without the functional water-soluble substance is shown in Table 3. However, the water absorption measurement of Examples 7 and 8 was omitted because the sample before coating was Example 4.

  Ascorbic acid, which is a functional water-soluble substance, could be gradually released from the granular material by using a hydrophilic substance in either a water-insoluble resin or a structural material and holding them. In addition, those particles coated with resin were much more slowly released than those without coating, and ascorbic acid, a functional water-soluble substance, could be released over a long period of time.

Example 9
A water-dispersible urethane resin water-based emulsion that is a water-insoluble resin, ascorbic acid that is a functional water-soluble substance, and pulp fibers that are a structural material are mixed in a high-speed agitation granulator (( A resin composition is obtained by adding and mixing to Dalton Co., Ltd. product: SPG-25), and this is tableted and dried with a rotary tableting machine (manufactured by Hata Iron Works Co., Ltd .: HT-AP18). A cylindrical pellet-like granular material having a size of 4 mm and a height of 4 mm was obtained.

(Example 10)
The granular material obtained in Example 9 was surface-coated with a urethane resin aqueous emulsion using a sugar coating machine (manufactured by Hata Iron Works Co., Ltd .: HC-200), water was evaporated, and the weights listed in Table 4 A granular material with a ratio was obtained.

(Result 3)
When the strength test was conducted, none of these granular materials remained unchanged in shape. Moreover, when the elution rate was calculated, it was as shown in Table 4, and ascorbic acid could be gradually released in all cases. In addition, Example 10 was able to release ascorbic acid for a longer time than Example 9 that was not coated. Further, Table 4 shows the water absorption of Example 9 which was molded without adding a functional water-soluble substance.

  Even in the granular material obtained by tableting, ascorbic acid, which is a functional water-soluble substance, could be gradually released as in the granular material obtained by extrusion granulation. In addition, Example 10 coated with resin released more slowly than Example 9 which was not coated, and was able to release ascorbic acid, which is a functional water-soluble substance, over a long period of time.

Claims (4)

It is composed of a resin composition containing a water-insoluble resin, a structural material and a functional water-soluble substance, and these are dispersed with each other,
The content ratio of the functional water-soluble substance in the resin composition is 20 to 90% by weight,
A functional water-soluble substance sustained-release material, wherein at least one of the structural material and the water-insoluble resin is hydrophilic.   The functional water-soluble substance sustained-release material according to claim 1, which is obtained by granulating the resin composition.   The functional water-soluble substance sustained-release material according to claim 2, wherein after granulating the resin composition, the surface of the obtained granulated material is coated with a resin.   The functional water-soluble substance sustained-release material according to any one of claims 1 to 3, wherein the functional water-soluble substance is ascorbic acid.