JPS62201156A - Base material including gradual release substance - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a base material containing a sustained-release substance, and more specifically to a substrate containing a sustained-release substance, such as a bactericide, an insecticide, a repellent, an attractant, a deodorant, or a fragrance. The present invention relates to a base material containing a sustained release substance which is desirably resistant to long-term effects and maintains its efficacy for a long period of time.

[Conventional technology]

As is well known, sustained release substances such as disinfectants are used in various fields, and it is desirable that these substances gradually volatilize and maintain their effectiveness for as long as possible. Conventionally, these sustained-release substances have been used as they are or supported on an appropriate air-permeable base material, but because the sustained-release substances are in direct contact with air, they volatilize quickly and are difficult to sustain for a long period of time. It was something.

Furthermore, recently, it has become common practice to install a base material carrying a sustained-release substance in a part of the ventilation path of various devices such as heaters and coolers that have a ventilation device. For example, as shown in Figure 1, a type of package has been developed in which granules of a sustained-release substance (2) are enclosed in an air-permeable bag (1), and this package can be attached as is to the ventilation path of a heater or cooler. It is something. In addition, (3) in Figure 1 is a part of the bag-like material that has been nailed into two parts, and a fine air-permeable base material (4 ) Pre-wrapped fine granular sustained-release substance inner packaging (5
) are stored. Such puff cages also have the disadvantage that their sustained effect is short because the sustained release substance is in direct contact with the air.

[Problem that the invention seeks to solve]

The problem to be solved by the present invention is to solve the above-mentioned difficulties of this type of sustained-release substance.In other words, by providing a base material containing a sustained-release substance with a large sustained effect. be.

[Means for solving problems]

The above problem can be solved by encapsulating the sustained release substance in inorganic microcapsules, granulating this together with a binder resin, and supporting this granule on an air permeable base material. By supporting inorganic microcapsules encapsulating on an air-permeable base material, preferably a sheet-like base material, and forming an adhesive layer consisting of an adhesive and inorganic microcapsules containing an adhesive dissolving agent on the surface thereof. achieved. [flI] The present invention provides a sustained-release substance-containing substrate characterized in that an air-permeable substrate supports particulate matter consisting of inorganic microcapsules encapsulating a sustained-release substance and a binder resin, and An adhesive layer consisting of an adhesive and inorganic microcapsules containing an adhesive dissolving agent inside is formed on one surface of an air-permeable sheet-like base material carrying inorganic microcapsules containing a release substance. The present invention relates to a sheet-like base material containing a sustained-release substance, characterized in that a release layer and a protective coating layer are further formed in this order on the pressure-sensitive adhesive layer, if necessary.

[Structure and operation of the invention]

The sustained-release substance-containing substrate according to the invention described in claim 1 of the present invention (hereinafter referred to as the first invention) is basically as follows.

(b) encapsulating a sustained-release substance in inorganic microcapsules, (b) granulating the microcapsules of (a) above with a binder resin to form granules, and (c) making the granules air permeable. It consists of being supported on a base material.

In the present invention, by encapsulating the sustained-release substance in inorganic microcapsules, one of the sustained-release substances
One loss is carried out gradually, and its lasting effect is significantly improved. In addition, by granulating inorganic microcapsules containing sustained-release microcapsules together with a binder resin, volatilization of the sustained-release substance is further suppressed, the divisor effect is further extended, and granular materials should not be carried. As the air-permeable base material, it is possible to use a material with a coarse mesh that prevents the granules from falling out or becoming scorched between the base materials. This facilitates the flow of air between the base materials, and the sustained release material is diffused by the air. Note that if a very dense substrate is used, air circulation will be insufficient, and even though the sustained release substance will volatilize, its diffusion will be insufficient.

The present invention will be explained in detail below in the order of (a) to (c).

The sustained-release substance is not particularly limited, and any substance that exhibits its effect by gradual decomposition can be used, such as contagious agents, insecticides, fragrances, deodorants, and other disinfectants. Examples include repellents for earthworms such as cockroaches and mosquitoes, and attractants such as pheromones. As the inorganic microcapsules to encapsulate the sustained release substance, microcapsules made of inorganic materials can be used, and the following are representative examples thereof.

In the present invention, the inorganic materials (referred to as wall materials) constituting the outer wall of the microcapsules include the following, and their IJ! Or use two or more types.

Alkaline earth carbonates: calcium carbonate, barium carbonate, magnesium carbonate, etc.

Alkaline earth metal silicates: calcium silicate, barium silicate, magnesium silicate, etc.

Alkaline earth metal phosphate...calcium phosphate,
Barium phosphate, magnesium phosphate, etc.

Alkaline earth metal sulfates: calcium sulfate, barium sulfate, magnesium sulfate, etc.

Gold g, M compounds: silica (anhydrous silicon PIi), titanium oxide, iron oxide, cobalt oxide, zinc oxide, nickel oxide, manganese oxide, aluminum oxide (alumina), etc.

Metal hydroxides: iron hydroxide, nickel hydroxide, aluminum hydroxide, calcium hydroxide, chromium hydroxide, etc.

Silicates other than alkaline earth metals: zinc silicate, aluminum silicate, silicate steel, magnesium aluminum silicate, magnesium silicate, etc.

Carbonates other than alkaline earth metals: zinc carbonate, aluminum carbonate, cobalt carbonate, basic copper carbonate, nickel carbonate, etc.

The method for encapsulating the sustained-release substance in the microcapsules is not limited to any manufacturing method as long as the sustained-release substance is encapsulated in the microcapsules.
For example, it can be manufactured by the following method.

Containing at least one inorganic compound selected from silicates, carbonates, phosphates and copper sulfates of alkali gold mud and halides of alkaline earth metals at a concentration of 0.3 sol/
J- Disperse the sustained release substance in a saturated aqueous solution. Next, mix an organic solvent with a water solubility of preferably 5% or less to form a W10 type emulsion, and then disperse alkaline earth metal halides, inorganic An acid, an organic acid, an aluminum salt of an inorganic acid, at least one of an ammonium salt of an organic acid and a carbonate of an alkali gold mud, and is formed into a water-insoluble precipitate (!!I) by an aqueous reaction with the above-mentioned inorganic compound. an aqueous solution (concentration 0.05 mol/l) of a compound capable of forming a substance)
- saturation concentration, preferably 0.1 to 2IIIO1/1) is mixed with the W10 type emulsion at a ratio equal to or higher than the latter to 100 parts by weight of the former. Thus, spherical porous inorganic-walled microcapsules containing a sustained-release substance are obtained. Examples of organic solvents with a solubility in water of 5% or less include aliphatic saturated hydrocarbons such as hexane, decane, hexadecane, isohexane, and isohebutane; aliphatic unsaturated hydrocarbons such as hexene, octene, dimethylpucdiene, and heptyne; Examples include aromatic hydrocarbons such as benzene, toluene, dodecylbenzene, cymene, and styrene; alicyclic hydrocarbons such as cyclohexane, cyclohexene, and cyclononane, and these may be used alone or in combination of 2ai or more. Also, is this equivalent amount tJ31? There is no problem even if up to about 10% by weight of alcohols etc. are mixed in the medium.The amount of organic solvent used is not particularly limited as long as the resulting emulsion is W2O type, but usually milk It is preferable that the amount is 5011% or more, preferably 70 to 80% by weight of the suspension. The emulsifying method may be any conventional method such as stirring or shaking. During emulsification, a known emulsifier can be added. As the emulsifier, nonionic surfactants preferably having an HLB in the range of 3.5 to 6.0 can be used, such as polyoxyethylene sorbicun monooleate,
Typical examples include polyoxyethylene sorbitan monolaurate, sorbitan monostearate, and sorbitan triolate. These emulsifiers are usually used in an amount of 5% by weight or less, preferably 0.01 to 3% by weight, based on the organic solvent.Such a manufacturing method is based on the procedure disclosed in Japanese Patent Publication No. 54-6251. It can be implemented according to the following.

Next, in the present invention, microcapsules containing a sustained release substance are mixed with a binder resin and granulated. In this case, the blending ratio of both microcapsules in the mixture is 50% by weight or less, preferably about 5 to 40% by weight. The particle size of the granulated granules is 1 to 10I@I11 as an average particle size.
The degree is preferably about 3 to 7III11. The binder resin used is wide (various natural or synthetic resins can be used, but synthetic resins are usually used. Typical examples include polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyethylene, polypropylene, and polyvinyl chloride. Methylpentene, polybutene-11 polybutadiene, polystyrene, acrylonitrile resin, As resin, ABS resin, MBS resin, polyphenylene ether, polyphenylene sulfate, fluororesin, silicone resin, polymethacrylstyrene and methacrylic resin, polyamide, polyimide, polyimide amide, polyethylene terephthalate , polybutylene terephthalate, polycarbonate,
Polyvinyl alcohol, polyvinyl ether, polyacetal, polyallylsulfone, polyarylate, isopropylene rubber, polybutadiene rubber, etc. In addition, two or more copolymers of these with other resins or other resins constituting these resins. Examples include blends of two or more polymers with each other or with other resins.

The shapes of granules are not limited to granular shapes (, pellet-like,
It includes various shapes such as a cylinder, a cone, a rectangular parallelepiped, and a cube.

The granules obtained by this process are supported on an air-permeable base material. Air-permeable base materials are widely used in this case, such as woven fabrics, non-woven fabrics, felt, n (oil), etc. An example is a base material etc. The supporting means is not particularly limited as long as the above-mentioned granular material is supported on the base material.

A typical method is to make the base material into a bag shape and encapsulate the granular material inside the bag-like base material. For example, the second
As shown in the figure, granules (7) are encapsulated in a bag-shaped base material (6).

Other forms of the present invention include the form described in claim 3 (referred to as the second invention). As shown in Fig. 13, this second invention is such that microcapsules (8) containing a sustained-release substance are supported on an air-permeable base material, preferably a sheet-like base material (9), and one surface thereof is An adhesive Jiii (10) is formed, and a release agent if (11) and a coating layer (
12). At this time, the above adhesive Fii
i (10) consists of an inorganic microcapsule (13) encapsulating an adhesive dissolving agent and an adhesive. The microcapsules encapsulating the sustained-release substance and the air-permeable base material used in the second invention are the same as those in the first invention, but the base material is sorted. The amount of microcapsules to be carried on the base material is particularly preferably about 0.11 to 80% by weight, preferably about io to 50% by weight, and is usually supported inside the base material sheet by an appropriate means. For example, when the base material is a synthetic resin sheet, a typical example is a method of embedding the microcapsules with or without protruding into the sheet, and when the base material is a woven fabric or non-woven fabric, an appropriate adhesive can be used. Examples include means for supporting the material in a woven fabric or non-woven fabric with or without using a woven fabric or a non-woven fabric with or without partially protruding. Although the microcapsules may be present uniformly within the base material, it is preferable that a large amount of the microcapsules be present on the surface opposite to the adhesive layer (10). In addition, in the present invention, granules of sustained-release microcapsules and binder resin can be used instead of sustained-release microcapsules, and the granules used in the first invention can be used as they are. Can be used.

The adhesive used as the component of adhesive N (10) can be any adhesive conventionally used in adhesive tapes. The solubilizer for the adhesive is one that can melt or swell the adhesive, and a solvent for the adhesive is usually used.This solubilizer is encapsulated in inorganic microcapsules to form the adhesive layer (10). The means for encapsulating the solubilizing agent in the microcapsules and the microcapsules themselves are the same as in the first invention.The adhesiveness of the microcapsules containing the solubilizing agent The amount in the agent layer is usually 0.1~
The amount is about 80% by weight, preferably about 10 to 60% by weight.

In the present invention, it is preferable to further provide a mold release agent layer (11) on the surface of the adhesive layer (10) if necessary.

In this case, any release agent that has been conventionally used as a release agent for this type of adhesive tape can be used, and specific examples include silicone release agents and fluorine release agents. I can do it. This mold release agent layer (11) is provided so that the ri layer (12) further provided thereon can be easily peeled off from the adhesive layer (10) during use. be. The covering layer (12) is a protective layer for the adhesive layer (10) and is peeled off during use.As this covering layer, materials conventionally used in this type of adhesive tape are used, such as: Examples include synthetic resin sheet-like materials, woven fabrics, and non-woven fabrics.

When using the base material of this second invention, the release layer (11) and the coating layer (12) are peeled off and the adhesive layer (l
Use O) by adhering it to the designated place.

By doing so, the sustained release substance within the microcapsules encapsulated in the base material (8) gradually evaporates and exerts its effectiveness. In particular, in the present invention, since the dissolving agent embedded in the adhesive layer (10) is encapsulated in microcapsules, the dissolving agent gradually deviates from the microcapsules and melts the adhesive. The adhesive strength itself does not increase rapidly, but the adhesive strength gradually develops. Therefore, even if the base material is adhered to a predetermined location, the adhesive force is not particularly strong, so it can be easily peeled off afterwards.For example, even when the effect of the sustained release substance has diminished, the base material can be easily peeled off. can be replaced with a new base material. Also adhesive fi
If the microcapsules contained in g (10) are contained in a partially protruding manner, the adhesive area is reduced, the adhesive strength is further reduced, and subsequent peeling becomes even easier.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

Example 1 A substrate as shown in FIG. 2 was prepared. That is, a nonwoven fabric made of synthetic resin is used as a bag-like base material, and granules with an average particle size of 3 to 711 Il are used, which are made of 40 parts by weight of inorganic microcapsules containing a disinfectant therein and 60 parts by weight of polyvinyl chloride. did. However, the inorganic microcapsules were prepared as follows.

No. 3 sodium silicate 6.5 mol/1. Add 15g of fungicide to 83mjH and stir for 1 minute to disperse. Sorbitan monolaurate (Span-20) 30g/j! The mixture was poured into cyclohexane melt with a concentration of 167mjt and emulsified for 1 minute at 700r, p, m using an emulsifying machine. This was made in advance m ammonium carbonate 1.5 morph 1 50
0ml and stir gently for 20 minutes.

This is subjected to solid-liquid separation using a centrifugal sedimentation machine.

Separate into disinfectant, encapsulated silica (solid), solvent, reaction by-product (sodium carbonate) and aqueous solution (liquid) of unreacted ammonium bicarbonate.

The germicide-containing silica obtained in this way is a 5% slurry with a pH of 9.6, so in order to neutralize it, the germicide-containing silica produced in pure water is added to 0.1 mol/l.
Adjust the pH to 5-6 with malic acid.

The encapsulated silica is recovered using a centrifugal filter again.

The germicide-containing silica obtained in this way has a size of 1
It was 0 to 50μ.

Example 2 A sheet-like base material shown in FIG. 3 was prepared. However, a synthetic resin nonwoven fabric was used as the base material layer, and the same sterilizing agent-containing silica as in Example 1 was used.

Styrene-butadiene rubber was used as the adhesive, and benzene was used as the adhesive solubilizer. The amount of microcapsules (encapsulated silica) in the base material is 30 to 35% by weight, and the amount of encapsulated silica in the adhesive layer is 30 to 35% by weight. The encapsulated silica containing the adhesive dissolving agent was manufactured by the following method. That is, put silica that will become the outer wall in a vacuum chamber, reduce the pressure to below IIIHg, stop the vacuum pump, and gently put the dissolving agent into the vacuum chamber under reduced pressure to thoroughly mix the silica and the dissolving agent. After standing still for a period of time, the inside of the tank was returned to atmospheric pressure, and the dissolving agent was forced into the silica, and the remaining dissolving agent was removed using a centrifuge to produce dissolving agent-containing silica.

[Brief explanation of drawings]

FIG. 1 is a schematic view of a conventional package-like base material containing a sustained-release substance, and FIG. 2 is a schematic view of a bag-like base material that is an example of the base material of the present invention. Moreover, FIG. 3 shows a schematic diagram of a sheet-like base material showing another example of the base material of the present invention. l... Bag-like material 2... Granular material of sustained release substance 3... Part of the bag-like material 4... Air-permeable base material 5 ... Sustained release substance inner packaging 6 ... Bag-like base material 7 ... Granules 8 ... Microcapsules containing sustained release substance 9. ... Sheet-like base material 10 ... Adhesive layer 11 ... Translated eyebrows 12 ... Covering layer 13 ... Dissolution of adhesive Microcapsules containing drugs (or more)

Claims (4)

[Claims] (1) A sustained-release substance-containing substrate, characterized in that an air-permeable substrate supports granules consisting of inorganic microcapsules encapsulating a sustained-release substance and a binder resin. (2) The sustained-release substance-containing substrate according to claim 1, wherein the granular material is housed in a bag-like material made of an air-permeable substrate. (3) Adhesive consisting of an adhesive and inorganic microcapsules containing an adhesive solubilizer inside, on one side of an air-permeable sheet-like base material carrying inorganic microcapsules containing the sustained-release substance. 1. A sheet-like base material containing a sustained-release substance, characterized in that a release layer and a protective coating layer are further formed in this order on the pressure-sensitive adhesive layer, if necessary. (4) The sustained release substance is a bactericide, insect repellent, repellent, attractant,
The sustained-release substance-containing substrate according to any one of claims 1 to 3, which is at least one of a deodorant and a fragrance.