JPH01143801A - Disintegratable molded body - Google Patents

Abstract

PURPOSE:To obtain a molded body, consisting essentially of a mixture of a liquid sucking powdery molding assistant with a sublimable powder, by impregnating the above-mentioned molding assistant with a volatile liquid having action, such as mothproofing, insecticidal, germicidal, antifungal, deodorant, aromatic or rust preventive action. CONSTITUTION:A disintegratable molded body, consisting essentially of a mixture of (A) 100pts.wt. liquid sucking powdery molding assistant (e.g., calcium silicate) with (B) 300-10,000pts.wt. (preferably 300-1,500pts.wt.) sublimable powder (e.g., borneol, adamantane or camphor) and prepared by impregnating the ingredient (A) with a volatile liquid. This molded body is capable of slowly skeletonizing due to sublimation of the ingredient (B) therefrom by volatilizing the ingredient (C) having insecticidal, antifungal, deodorant action, etc., and finally disintegrating. Thereby the extent of the reduction in amount of the volatile liquid in the molded body and end point of the volatilization can be judged and period of changing can be precisely known. The volatilization of the ingredient (C) present therein is promoted by skeletonization with hardly any reduction in the amount volatilized.

Description

[Detailed description of the invention] [Industrial application field] The present invention is insect repellent, insecticidal, sterilizing, fungicidal, and deodorizing.

Contains volatile liquids that have aromatic or antirust effects,
The present invention relates to a collapsible molded product that becomes a skeleton over time as it volatilizes and eventually collapses.

[Conventional technology]

Conventionally, liquid-absorbing molded bodies have been impregnated with volatile liquids in order to prevent liquid leakage due to falls or breakage during use of containers filled with volatile liquids that have insect repellent or insecticidal effects. something is proposed.

However, the molded body impregnated with this volatile liquid,
There was a problem in that the shape of the molded body did not change even after most of the volatile liquid had evaporated, making it impossible to replace the molded body. In particular, when the efficacy of volatile liquids is difficult to discern by odor, color, etc.
The above problems were serious.

[Problem that the invention seeks to solve]

As a result of repeated research in order to solve these problems, the inventors of the present invention have developed a molded article composed of a liquid-absorbing powder molding aid and a specific amount of sublimable powder.

When the powdered molding aid is impregnated with a volatile liquid, the sublimable powder sublimes from the molded object as the volatile liquid evaporates, and the molded object gradually becomes a skeleton and collapses. The degree of reduction of volatile liquid in the molded body and the end point of volatilization can be visually checked]
The inventors have discovered that this can be determined, and have completed the present invention.

An object of the present invention is to provide a collapsible molded product that can determine the degree of decrease in the amount of volatile liquid in the molded product and the end point of volatilization by visual inspection or contact, and can reliably know when to replace the volatile liquid. Our goal is to provide the following.

[Means for solving problems]

That is, 1 the collapsible molded article of the present invention contains 100 parts (parts by weight, the same applies hereinafter) of a liquid-absorbing powder forming aid and 300 parts of a sublimable powder.
-10,000 parts.

The molding aid is also characterized in that the molding aid is impregnated with a volatile liquid.

The powdery molding aid used in the present invention is not particularly limited as long as it is a powder that can be pressure-molded by itself without using a binder (self-molding property) and has liquid absorption properties. As for liquid absorption, a liquid absorption amount of 3 (A/I or more) can be used, preferably a liquid absorption amount of 4cc77 or more.Also, the particle size of the powdered forming aid is not particularly limited, but generally Those having an average particle diameter of 100 .mu.m or less are preferred.An example of a typical powder forming aid used in the present invention is calcium silicate, which is described in JP-A No. 54-93698.

That is, the above-mentioned calcium silicate is a powder made of calcium silicate, which is formed of an aggregate of flakes having two opposing sides. Calcium silicate formed from an aggregate of flakes having two opposing surfaces is a special type of known calcium silicate and is manufactured by a limited manufacturing method. A typical manufacturing method is shown in the above-mentioned Japanese Patent Application Laid-Open No. 54-93698.

In addition, when water-soluble silicates such as sodium silicate and potassium silicate are used as raw materials and gypsum, the silicate is generally added gradually to the gypsum suspension and reacted, and the reaction system is used as it is or from the reaction system. Filter the reaction product.

It can be obtained by making the filtered product into a suspension again and then hydrothermally treating it at a temperature of 150 to 250°C. In these production methods, the size of the flakes obtained differs depending on the mixing ratio of raw materials, reaction conditions, etc. Generally, the most suitable calcium silicate can be obtained by mixing the raw materials so that the S 102 /CaO molar ratio of the obtained calcium silicate is 1.6 to 4.2. The calcium silicate obtained above has a gyrolite crystal structure. Also facing 2
It is made up of a collection of flakes with two sides. The shape can be confirmed by taking a microscopic photograph (for example, 5000 times magnification). Generally, the flakes constituting the calcium silicate have an average diameter in the longitudinal direction of 0.1 to 30 μm and a thickness of o to o.
Normally, it is in the range of os ~ 0.1μ, and industrially, the average diameter in the longitudinal direction is 0.5~15μ, and the thickness is o, oo.
From the micrograph of the above calcium silicate, which is most easily obtained, calcium silicate with a particle size of about s~0.1μ can be observed to have a shape in which the aggregated state of the flakes resembles a flower with aggregated petals, especially a para flower. For this reason, it is sometimes abbreviated as petal-shaped calcium silicate. Hereinafter, in this specification as well, calcium silicate having the above-mentioned properties may be abbreviated as petal-like calcium silicate.

The petal-shaped calcium silicate is disclosed in, for example, JP-A-54-936.
As shown in No. 98, it is a crystalline substance with a gyrolite type crystal structure, but depending on the mixing ratio of raw materials, it can become an amorphous 5to
This amorphous 5102, which often contains 2ft, cannot confirm grain boundaries even if micrographs of petal-shaped calcium silicate thin sections are taken at 10 times or more magnification. will be confirmed. Of course, gyrolite type calcium silicate is 2 Ca0.35
Since it is expressed as in2.2H20, the content of amorphous SiO2 can also be determined by chemically analyzing petal-shaped calcium silicate and calculating the Si02/CaO molar ratio. Generally, as mentioned above, petal-shaped calcium silicate, which is most easily obtained industrially, has an average diameter in the longitudinal direction of 0.1
~15μ and the thickness is 0.005~0.1μ, but such petal-shaped calcium silicate has SiO2/
Most of them have a CaO molar ratio in the range of 1.6 to 4.2.

Although the manufacturing method and shape of one typical petal-shaped calcium silicate have been described above, the present invention is not limited thereto, and any petal-shaped calcium silicate having the above-mentioned shape can be used without particular limitation.

In addition, a product obtained by contacting the petal-shaped calcium silicate with a mineral acid to remove calcium (hereinafter referred to as "calcium silicate").

Petal-like silica) can also be used as a powder forming aid in the present invention.

In addition, one example of the volatile liquid used in the present invention is:

Liquids that are volatile or evaporative under the intended use conditions, generally at room temperature and atmospheric pressure, or liquids that contain such liquids as active ingredients.

Selected appropriately.

For example, hinokitiol (β-thujapliein)
).

Cypress oil and cypress oil containing these; insect repellents such as Nautsuka oil, turpineol, spearmint oil, and α-limonene; insecticides such as eninsulin and dichlorges;
Noid, wood acetic acid, orunpenzenehalachlorphenol, plnan hydroperoxide
Deodorants such as s); pinene, myrcene.

Cineol, rose oxide, Cal-4-ol.

Fragrances such as isomenylacetate, milranal, monoalpha-pineol; dicyclohexylamine.

Rust inhibitors such as dicyclohexylamine fatty acid salts, dicyclohexylamine nitrite, 1-morpholine, benzotriazole, methylbenzotriazole, and amine salts of benzotriazole are included. Two or more of these volatile liquids can also be used in combination.

Further, as the sublimable powder used in the present invention, any powder in an amount that can be sublimed under the above conditions of use of the volatile liquid can be used without particular limitation. For example, if such usage conditions are at room temperature and atmospheric pressure.

? Cineol [1e'L7-Trim@tyl bia
yellow-(1e2s2)-heptan-2-ol
) *Adamantane (tricyclodecane), camphu 7
- (camphor) e-menthol (t-me
nthol) *Camph@ne and the like are preferably used. The particle size of the sublimable powder is not particularly limited, but generally has an average particle size of 1O-Zo.

μm is appropriate.

In the disintegrating molded article of the present invention, it is necessary that the sublimable powder be present in a ratio of 300 to 10,000 parts per 100 parts of the powdered molding aid, and the preferred ratio is 300 to 1,500 parts.
Department. When the proportion of the sublimable powder is less than 300 parts, the molded body is unlikely to collapse due to sublimation of the powder, and such collapse makes it difficult to judge the decrease in volatile liquid. Also, when the above ratio is 10,000 parts, the absolute amount of volatile liquid impregnated into the powdered forming aid decreases, -
It is not practical because the desired medicinal efficacy is reduced. Therefore, the proportion of the sublimable powder should be within the above range, taking into consideration the amount of volatile liquid present in the molded product, the volatilization rate, etc. All you have to do is decide on an appropriate ratio.

In addition, in the present invention, the amount of volatile liquid to be impregnated into the powdery molding aid is 50 to 10% of the liquid absorption amount of the powdery molding aid.
It is preferable to adjust the ratio to 0% by weight.

Furthermore, the collapsible molded article of the present invention may contain other powders, such as pigment powder, within a range that does not significantly reduce the moldability of the powdered molding aid.

The manufacturing method for obtaining the collapsible molded article of the present invention is not particularly limited, but pressure molding is common. For example, a powder molding aid is impregnated with a volatile liquid, this is uniformly mixed with sublimable powder, and then pressure molded using a mold of an appropriate size and shape, or powder molding is used. The auxiliary agent and the sublimable powder are uniformly mixed and pressure molded in the same manner as above, and then the resulting molded product is brought into contact with a volatile liquid by means such as immersion to remove the volatile liquid. A common method is to impregnate it with a powdered molding aid.

The molding pressure in the pressure molding described above varies somewhat depending on the type and proportion of the powdery molding aid used.

Generally, a range of 30 to 300 kp/cm'' is preferred.

Further, the shape of the desired disintegrating molded article is generally a tablet shape, a disk shape, a plate shape, a stick shape, etc., but is not limited to these shapes and can be arbitrarily determined.

In the present invention, the collapsible molded body is preferably determined so that the end point of volatilization of the volatile liquid impregnated into the collapsible molded body and the time of disintegration of the molded body almost coincide with each other.

Such adjustments can be made by using methods such as changing the amount of sublimable powder used, changing the amount of volatile liquid impregnated, and changing the molding pressure of the molded body within the above range, or by combining them as appropriate. You can have sex.

Since the collapsible molded article of the present invention gradually disintegrates and becomes powder during use, it is preferable to package it in a container having at least a portion of a porous film. It is preferable that the material has pores through which the components can pass, but which the powder cannot pass through. Generally J
100 measured using a Ga'-retensometer used in ISP8117 "Testing the air permeability of paper and paperboard, etc."
A film having a cc air passage time of 4,000 to 15,000 seconds is suitable. Specific examples include paper such as Japanese paper and synthetic paper.

Examples include laminated paper made of these plastics, porous propylene film, porous glass film such as porous polyethylene film, and the like. Further, the container is generally in the shape of a bag or a box.

〔Example〕

EXAMPLES In order to explain the present invention more specifically, Examples are shown below, but the present invention is not limited to these Examples.

Note that the remaining amount of volatile liquid and the collapse point were measured by the following method.

(1) Amount of remaining volatile liquid After extracting the volatile liquid in the sample using a Soxhlet extractor or an organic solvent, using gas chromatography)
Quantitated.

(2) Collapse point The sample was allowed to stand still, and the number of days required for the entire surface of the molded product to disappear was measured.

Example 1 As a powdered molding aid, the apparent specific gravity is 0.1011/cc, and the liquid absorption amount is scc/! Petal-shaped calcium silicate 1 (trade name Fluorite, manufactured by Tokuyama Ichisai Co., Ltd.) was used as the volatile liquid, and hiba oil was used as the volatile liquid.
A liquid-impregnated powder was obtained by mixing 00 parts of cypress oil and 00 parts of cypress oil in a Henschel mixer.

Next, as a sublimable powder, powder of a sublimable substance shown in Table 1 was mixed in the indicated ratio with respect to 100 parts of petal-like calcium silicate in the liquid-impregnated powder. Thereafter, the mixture was pressure-molded using a 20N cylindrical mold at a molding pressure of 300 mm/α2 to obtain 8 molded bodies each weighing 2I. ? : The molded products were left standing in a room at a temperature of 20° C. and a humidity of 65%, and after 4, 10, and 20 days, two molded products f were taken out and the remaining amount of volatile liquid was measured. In addition, the collapse point of the remaining two molded bodies was measured, and the amount of volatile liquid remaining at the time of collapse was also measured. The results are also shown in Table 1.

Example 2 In implementation f141, petal-shaped calcium silicate 100
The sublimable powder used was Reneol at a ratio of 400 parts to 400 parts, and the type of volatile liquid was changed to
A molded body was obtained in the same manner as Example 5 of Example 1a except for the changes shown in the table. It takes 11ksI for this one molded body:
L> and the amount of volatile noodles remaining at the time of disintegration were measured. *The results are also shown in Table 2.

Table 1 -41 is a comparative example.

Table 2 [Effects of the Invention] The disintegrating molded article of the present invention has a volatile liquid as an active ingredient.
As the sublimable powder sublimates as it evaporates, the molded body gradually becomes a skeleton, and eventually collapses and becomes powder. Therefore, the degree of decrease in the amount of volatile liquid and the end point of volatilization can be determined visually or by contact, and the time to replace the liquid can be known with certainty. In addition, the volatilization of the volatile liquid present inside the molded object is promoted, and the decrease in the amount of volatilization is small, and the end point of volatilization is A uniform effect can be obtained.

In addition, in the present invention, it is preferable to use substances with low acute oral toxicity such as borneol, adamantane, t-menthol, and can-7ene as the sublimable powder, and to use natural plant extracts such as hinokitiol as the insect repellent component. Ba,
Balajichlorobenzene, conventionally known as an insect repellent,
It is possible to form an insect repellent that is extremely safe compared to naphthalene, schizophrenia, and the like.

Agent Patent Attorney Johei Yamashita

Claims (1)

[Claims] 100 parts by weight of liquid-absorbing powder molding aid and 300 parts by weight of sublimable powder
10,000 parts by weight of a disintegrating molded article, the disintegrating molded article is mainly composed of a mixture of 10,000 parts by weight and the above-mentioned molding aid is impregnated with a volatile liquid.