JPH0762130B2 - Sheet-like base material containing sustained-release substance - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a base material containing a sustained-release substance, and more specifically, it is effective as a fungicide, insecticide, repellent, attractant, deodorant or fragrance by gradually evaporating. The present invention relates to a base material containing a sustained-release substance that is desired to last for a long period of time.

[0002]

BACKGROUND OF THE INVENTION As is well known, sustained-release substances such as bactericides are used in various fields, and it is desirable that these substances are gradually volatilized so that their effects last as long as possible. Conventionally, these sustained-release substances are used as they are or by supporting them on an appropriate air-permeable base material, but since the sustained-release substance is in direct contact with air, its volatilization is rapid and it is difficult to last for a long time. It was a thing.

In addition, recently, in each device having a blower such as a heater or a cooler, a base material carrying a sustained release substance has been installed in a part of a blower path. For example, as shown in Fig. 1, a type of package was developed in which a granular material (2) of a sustained release material was enclosed in an air-permeable bag-like material (1), which was directly attached to the ventilation path of a heater or cooler. Is. In addition, (3) in FIG. 1 is a part in which the bag-like material is sandwiched between two parts, and there is an air-permeable base material (4) having a fine mesh so that other sustained-release substances do not volatilize due to the blowing of air. A fine-grained sustained-release substance-containing bag (5) pre-wrapped with is stored. Also in such a package, the sustained-release substance is in direct contact with air, so that the sustaining effect thereof is short.

[0004]

Problems to be Solved by the Invention The problem to be solved by the present invention is to solve the above-mentioned drawbacks of this type of sustained-release substance, in other words, a sustained-release substance having a large sustained effect. It is to provide a base material that encapsulates.

[0005]

[Means for Solving the Problems] The above problems are caused by supporting inorganic microcapsules encapsulating a sustained-release substance on an air-permeable sheet-like substrate, and one surface of the inorganic microcapsules containing a dissolving agent for an adhesive. And an adhesive layer. That is, the present invention is a pressure-sensitive adhesive comprising an inorganic microcapsule containing a dissolution agent of an adhesive therein and an adhesive on one surface of an air-permeable sheet-shaped substrate carrying an inorganic microcapsule containing a sustained-release substance. The present invention relates to a sustained-release substance-encapsulating sheet-like base material, which comprises forming an agent layer and, if necessary, further forming a release layer and a protective coating layer on the pressure-sensitive adhesive layer in this order.

[0006]

As shown in FIG. 2, the present invention supports microcapsules (8) containing a sustained-release substance on an air-permeable substrate, preferably a sheet-shaped substrate (9). The pressure-sensitive adhesive layer (10) is formed on the surface, and the release agent layer (11) and the coating layer (12) are formed on the pressure-sensitive adhesive layer (10) if necessary. At this time, the pressure-sensitive adhesive layer (10) is composed of an inorganic microcapsule (13) in which a dissolving agent for the pressure-sensitive adhesive is encapsulated and a pressure-sensitive adhesive.

First, the microcapsules containing the sustained-release substance and the air-permeable substrate used in the present invention will be described.

The sustained-release substance is not particularly limited, and any substance that can be volatilized gradually to exert its effect can be used. For example, a bactericidal agent, an insecticide, a fragrance, a deodorant, and other substances. Fungicides, repellents for insects such as cockroaches and mosquitoes,
Examples thereof include attractants such as pheromones. As the inorganic microcapsules for encapsulating the sustained-release substance, microcapsules made of an inorganic material can be used, and typical examples thereof include the following.

In the present invention, the inorganic material forming the outer wall of the microcapsule (referred to as wall material) is
The following are mentioned, and 1 type (s) or 2 or more types are used.

Alkaline earth metal carbonates ... Calcium carbonate, barium carbonate, magnesium carbonate, etc.

Alkaline earth metal silicate ... Calcium silicate, barium silicate, magnesium silicate, etc.

Alkaline earth metal phosphate ... Calcium phosphate, barium phosphate, magnesium phosphate, etc.

Alkaline earth metal sulfate ... Calcium sulfate, barium sulfate, magnesium sulfate and the like.

Metal oxide: Silica (silicic acid anhydride), titanium oxide, iron oxide, cobalt oxide, zinc oxide, nickel oxide, manganese oxide, aluminum oxide (alumina), etc.

Metal hydroxide: Iron hydroxide, nickel hydroxide, aluminum hydroxide, calcium hydroxide, chromium hydroxide, etc.

Silicates other than alkaline earth metals: zinc silicate, aluminum silicate, copper silicate, 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 of encapsulating the sustained-release substance in the microcapsules is not limited as long as the sustained-release substance is encapsulated in the microcapsules, but the method is not limited to the following. Can be manufactured by.

A concentration of 0.3 m containing at least one inorganic compound selected from alkali metal silicates, carbonates, phosphates and copper sulfates and alkaline earth metal halides.
Disperse the sustained-release substance in an aqueous solution of ol / l to saturated. Then, a W / O type emulsion is prepared by mixing an organic solvent having a solubility in water of preferably 5% or less, and then a halide of an alkaline earth metal, an inorganic acid, an organic acid, an ammonium salt of an inorganic acid, an organic acid. Of at least one of ammonium salts and carbonates of alkali metals, which is water-insoluble by the reaction with an aqueous solution of the above-mentioned inorganic compound (ie, wall substance)
An aqueous solution of a compound capable of forming (a concentration of 0.05 mol / liter to a saturated concentration, preferably 0.1 to 2 mol / liter,
The W / O type emulsion is mixed with 100 parts by weight of the former in an amount equal to or more than the latter. Thus, spherical porous inorganic wall microcapsules containing the sustained-release substance are obtained.

Organic solvents having a solubility in water of 5% or less include hexane, decane, hexadecane isohexane, isoheptane, and other saturated aliphatic hydrocarbons: hexene,
Aliphatic unsaturated hydrocarbons such as octene, dimethyl butadiene and heptin: Benzene, toluene, dodecylbenzene, cymene, aromatic hydrocarbons such as styrene: cyclohexane, cyclohexene, alicyclic hydrocarbons such as diclononane, and the like. Are used alone or in combination of two or more.

In addition, it does not matter if these organic solvents are mixed with alcohols or the like up to about 10% by weight. The amount of the organic solvent used is not particularly limited as long as the obtained emulsion is a W / O type, but it is usually 50% by weight or more, preferably 70 to 80% by weight of the emulsion.

The emulsion method may be a conventional method such as a stirring method or a shaking method. Upon emulsification, a known emulsifier can be added. As the emulsifier, a nonionic surfactant having an HLB of 3.5 to 6.0 can be preferably used, and polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monolaurate, sorbitan monostearate, sorbitan can be used. A typical example is trio rate. These emulsifiers are usually used in an amount of 5% by weight or less, preferably about 0.01 to 3% by weight, based on the organic solvent. Such a manufacturing method can be carried out according to the procedure disclosed in Japanese Patent Publication No. 54-6251.

As the air permeable base material, air permeable base materials are widely used, and examples thereof include woven cloth, non-woven cloth, felt and resin base material. A sheet-shaped material is used as the base material.

The amount of microcapsules to be supported on this substrate is usually 0.1 to 80% by weight, preferably 10
It is about 50% by weight, and it is usually supported inside the base material sheet by an appropriate means. For example, when the base material is a synthetic resin sheet, a means for embedding the microcapsules can be illustrated as a typical example without partially protruding or not protruding into the sheet, and when the base material is a woven cloth or a non-woven cloth, an appropriate adhesive is used. There may be mentioned a means for supporting the woven or non-woven fabric with or without an agent in a partially or partially protruding manner.

The microcapsules may be present uniformly in the substrate, but it is preferable that a large amount of microcapsules be present on the surface opposite to the pressure-sensitive adhesive layer (10).

In the present invention, instead of the sustained-release microcapsules, granules of the sustained-release microcapsules and the binder resin can be used. Examples of the granules include the following.

For example, microcapsules containing a sustained-release substance are mixed with a binder resin and granulated.
In this case, the mixing ratio of both is 50% by weight or less, preferably about 5 to 40% by weight, of the microcapsules in the mixture.
The average particle size of the granulated granules is about 1 to 10 mm, preferably about 3 to 7 mm.

As the binder resin used, a wide variety of natural or synthetic resins can be used, but synthetic resins are usually used. Typical examples are polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyethylene, polypropylene, polymethylpentene, polybutene-1,
Polybutadiene, polystyrene, acrylonitrile resin, AS resin, ABS resin, MBS resin, polyphenylene ether, polyphenylene sulfate, fluororesin, silicone resin, polymethacrylstyrene, methacryl resin, polyamide, polyimide, polyimide amide,
Polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl alcohol, polyvinyl ether, polyacetal, polyallyl sulfone, polyarylate, isopropylene rubber, polybutadiene rubber and the like, and two or more kinds of monomers constituting these resins or other resins And a blend of two or more of these copolymers with each other or with other resins.

The shape of the granular material is not limited to the granular shape,
Various types such as pellets, cylinders, cones, cuboids and cubes are included.

The pressure-sensitive adhesive used as one component of the pressure-sensitive adhesive layer (10) may be the pressure-sensitive adhesive that has been conventionally used for pressure-sensitive adhesive tapes. The solvent for the pressure-sensitive adhesive is capable of dissolving or swelling the pressure-sensitive adhesive, and a solvent for the pressure-sensitive adhesive is usually used. The dissolving agent is enclosed in an inorganic microcapsule and partially embedded in the pressure-sensitive adhesive layer (10) or embedded without protruding. At this time, the means for encapsulating the dissolving agent in the microcapsules is the same as the means for encapsulating the sustained-release substance in the microcapsules. The amount of the microcapsules containing the dissolving agent in the adhesive layer is usually 0.1 to 80% by weight, preferably 10 to 60% by weight.
It is a degree.

In the present invention, it is preferable to further provide a release agent layer (11) on the surface of the pressure-sensitive adhesive layer (10) if necessary. As the release agent at this time, any of those conventionally used as a release agent for this kind of adhesive tape can be used, and specific examples thereof include a silicone-based release agent and a fluorine-based release agent. I can.

This release agent layer (11) is used as a pressure-sensitive adhesive layer (1) when a coating layer (12) further provided thereon is used.
It is provided for easy peeling from (0). The coating layer (12) is a protective layer for the pressure-sensitive adhesive layer (10) and is peeled off at the time of use. As this coating layer, those conventionally used for this type of pressure-sensitive adhesive tape are used. Examples include synthetic resin sheet materials, woven fabrics, and non-woven fabrics.

When using the base material of the present invention, the release layer (11) and the coating layer (12) are peeled off and the pressure-sensitive adhesive layer (1
Use 0) by sticking it in place. By doing so, the sustained-release substance in the microcapsules encapsulated in the base material (8) is gradually volatilized to exert its effect.

Particularly in the present invention, since the dissolving agent embedded in the pressure-sensitive adhesive layer (10) is encapsulated in the microcapsules, the dissolving agent gradually deviates from the microcapsules and dissolves the adhesive. Therefore, the adhesive force of the adhesive is gradually exhibited without the adhesive force itself of the adhesive being rapidly increased.
For this reason, even if the base material is adhered to a predetermined place, the adhesive force is not particularly large, so that the base material can be easily peeled off thereafter. Can be replaced with a new base material. Further, when the microcapsules contained in the pressure-sensitive adhesive layer (10) are partly projected and contained, the pressure-sensitive adhesive area is reduced, the pressure-sensitive adhesive force is further reduced, and the subsequent peeling is further facilitated.

[0035]

The present invention will be described in more detail with reference to the following examples.

[0036]

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

No. 3 sodium silicate 6.5 mol / liter, 8
Add 15g of germicide to 3ml, stir for 1 minute to disperse,
Sorbitan monolaurate (Span-20) 30g /
It is placed in 167 ml of cyclohexane solution having a concentration of 1 liter and emulsified by an emulsifier at 700 rpm for 1 minute. 1.5 mol of ammonium bicarbonate prepared in advance /
Place in 500 ml liter and stir gently for 20 minutes.

This is subjected to solid-liquid separation using a centrifugal settler. Separate the aqueous solution (liquid) layer of the bactericide, encapsulated silica (solid), solvent, reaction by-product (sodium carbonate) and unreacted ammonium bicarbonate.

The bactericide-containing silica thus obtained had a pH of 9.6 with a 5% slurry, so that the bactericide-containing silica produced in pure water was added to neutralize the silica.
Adjust the pH to 5-6 with 1 mol / l malic acid.
The encapsulated silica is recovered again by a centrifugal filter.

The silica containing bactericide thus obtained had a size of 10 to 50 μm. Styrene-butadiene rubber was used as the adhesive and benzene was used as the dissolving agent for the adhesive. The amount of microcapsules (encapsulated silica) in the substrate 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, after putting silica as the outer wall in the vacuum chamber and reducing the pressure to 1 mmHg or less, stop the vacuum pump and gently put the dissolving agent in the vacuum chamber under the reduced pressure to sufficiently mix the silica and the dissolving agent. After standing for a while, the pressure in the tank was returned to atmospheric pressure, the dissolving agent was pressed into the silica, and the remaining dissolving agent was removed by a centrifuge to produce a dissolving agent-containing silica.

[Brief description of drawings]

FIG. 1 is a schematic view of a conventional sustained-release substance-containing bag-shaped substrate.

FIG. 2 is a schematic view of a sheet-shaped substrate showing an example of the substrate of the present invention.

[Explanation of symbols]

 1-Bag-like material 2-Granular material of sustained-release material 3-Part of bag-like material 4-Air-permeable base material 5 --- Sustained-release substance-containing bag 8 --- Microcapsules containing sustained-release substance 9 --- Sheet-shaped substrate 10 --- Adhesive layer 11 ... ..Release layer 12 ... Coating layer 13 ... Microcapsules containing adhesive dissolution agent

Claims (2)

[Claims] 1. A surface of an air-permeable sheet-like base material carrying inorganic microcapsules containing a sustained-release substance,
A sustained-release substance-encapsulating sheet-like base material, comprising a pressure-sensitive adhesive layer formed of an inorganic microcapsule containing a pressure-sensitive adhesive dissolving agent therein and a pressure-sensitive adhesive. 2. The sustained-release substance is at least one of a bactericide, insect repellent, repellent, attractant, deodorant and fragrance.
The sheet-shaped base material containing the sustained-release substance described in 1.