JPH08267615A - Synthetic resin molded article and production thereof - Google Patents

Abstract

PURPOSE: To obtain a synthetic resin molded article having a nauseating action for preventing him/her from choking if it is put in his/her mouth by a method wherein a communicating porous holding body with a nauseant held in its communicating pores is provided on the surface. CONSTITUTION: A synthetic resin molded article is formed by molding a synthetic resin material by a mold for extruding or injection molding. The synthetic resin material is prepared by loading and kneading a synthetic resin as a base with a communicating porous holding body. At this time, molding is conducted under the condition that the temperature of the mold is relatively low on the outer side thereof and relatively high on the inner side thereof, whereby a communicating porous holding body 4 can be exposed on an outer surface 3 of the molded article. A nauseant dissolved, for example, in a solvent is held in the communicating porous holding body 4 exposed on the outer surface 3 of the molded article.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to molded articles such as extrusion molding and injection molding of synthetic resins such as polyvinyl chloride, polyethylene, polypropylene and polyethylene terephthalate, and a manufacturing method thereof.

[0002]

2. Description of the Related Art Synthetic resin moldings are often used for toys and writing instruments such as caps and exterior bodies, and are often used by children. For example, a groove is formed to secure a breathing airflow passage.

[0003]

However, the above-mentioned air flow passage tends to act only in a certain direction, and in the case of a shape close to a cube or a sphere, the air flow passage for breathing cannot always be secured. .

Even if the air passage for breathing can be secured, it must be finally removed from the throat, and at that time, the inner wall of the throat may be damaged, which is a safety aspect. The current situation is that I am not very satisfied.

[0005]

[Means for Solving the Problems] Since a synthetic resin molded product is put in the mouth, there is a risk of suffocation. Therefore, even if it is put in the mouth, it is necessary to immediately exhale. . That is, the gist of the present invention is a synthetic resin molded article obtained by supporting an emetic agent on the surface of the communicating porous support of the communicating porous support, and disposing the communicating porous support carrying the emetic on the surface. .

The present invention will be described in more detail below. A synthetic resin material in which a communicating porous carrier is added to a synthetic resin as a base material and kneaded is molded by a mold for extrusion molding or injection molding.
At this time, when the temperature of the mold is molded under the condition that the temperature of the outer mold is relatively low and the temperature of the inner mold is relatively high, the communicating porous carrier can be exposed on the outer surface of the molded product. . The communicating porous carrier exposed on the outer surface of the molded article carries the emetic agent dissolved in a solvent. If it is stable against heat, such as the decomposition temperature of the emetic carried is high,
It is also possible to mix what was previously supported on the communicating porous support with the synthetic resin that is the base material, but if you want to support it in the state of an aqueous solution or if the decomposition temperature of the emetic agent is low, load it after molding. Need to let. Specific examples of synthetic resin molded products include toy parts, caps, tail plugs,
Examples thereof include parts for writing tools and applicators such as outer casings, parts for containers such as caps for paint containers, and synthetic rubber moldings such as eraser.

Further, a continuous porous carrier carrying an emetic agent is mixed with an ink for printing or the like, and the ink is used to coat the outer wall of the molded product or to print it to produce a synthetic resin molded product. It is also possible to place an emetic agent on the surface of the. When a child mistakenly puts the synthetic resin molded product thus produced in his mouth, the bitterness immediately spreads in his mouth, and the molded product put in his mouth is spit out.

The continuous porous carrier is used for holding the emetic agent on the surface of the synthetic resin molded article, and any material which can retain the emetic agent in the solution or solid state can be used. Silica gel communication porous support, diatomaceous earth communication porous support, glass communication porous support, activated carbon communication porous support, zeolite communication porous support, cellulose communication porous support, high-grade water-soluble resin support, etc. Can be mentioned.

As the emetic agent, a bitterness emetic agent such as denatonium benzoate (molecular formula C ₂₈ H ₃₄ N ₂ O ₃ , melting point 1
63-170 ° C), etc. as sourness-emetics, citric acid, tartaric acid, lactic acid, acetic acid, glacial acetic acid, fumaric acid, sodium fumarate, malic acid, adipic acid, etc. Examples include oat, β-sanshool, zingerone, shogaol, isothiocyanate and the like. In terms of the emetic action when contained in the mouth, it is considered that bitter emetics are particularly effective, but when denatonium benzoate is used, methanol, ethanol, chloroform, butanol, isopropanol, acetone, methyl ethyl are used as the solvent. Examples thereof include toluene, benzene, toluene and water. When dissolved in an organic solvent, from the viewpoint of safety, it is necessary to add the product to a synthetic resin molded product and then sufficiently dry it to volatilize the solvent before use.

[0010]

EXAMPLES An example will be described below. Example 1 Tonen Polypro J215 (polypropylene resin, manufactured by Tonen Chemical Co., Ltd.) was added with 1.0% by weight of a silica gel continuous porous carrier (average particle size: 5 μm, manufactured by Fuji Silysia Ltd.). Thus, a writing instrument cap made of a bottomed cylinder having a circular cross section was molded with an injection molding mold in which the temperature of the outer mold (cavity) was 20 ° C and the temperature of the inner mold (core pin) was 30 ° C. BIRTEX (bitter emetic,
Denatonium benzoate, Macfarlan Sm
80 ± 2 ° C in which 50 ppm of ith, UK) was dissolved
After soaking the cap in an aqueous solution and treating it for 15 minutes while stirring so that the liquid and the entire cap come into contact, remove from the aqueous solution and wipe off the aqueous solution on the surface, silica gel continuous porous support partially exposed on the surface BITR inside the body
A polypropylene cap carrying an EX aqueous solution was obtained.

Example 2 The amount of BITREX added in Example 1 was changed from 50 ppm to 10 p.
In the same manner as in Example 1, instead of pm, BI is placed inside the silica gel-containing porous support having a partially exposed surface.
A polypropylene cap carrying a TREX aqueous solution was obtained.

Example 3 The amount of BITREX added in Example 1 was changed from 50 ppm to 100.
In the same manner as in Example 1 except that ppm is replaced with B in the silica gel communicating porous support which is partially exposed on the surface.
A polypropylene cap carrying an ITREX aqueous solution was obtained.

Example 4 The addition amount of the silica gel continuous porous carrier of Example 1 was 1.0.
In the same manner as in Example 1, except for changing from wt% to 0.1 wt%, a polypropylene cap having a BITREX aqueous solution supported inside a silica gel communicating porous support having a part exposed on the surface was obtained.

Example 5 The addition amount of the porous silica-supported porous carrier of Example 1 was 1.0.
In the same manner as in Example 1, except for changing from 0.5% by weight to 0.5% by weight, a polypropylene cap having a BITREX aqueous solution supported inside a silica gel communicating porous support having a partially exposed surface was obtained.

Example 6 The ion-exchanged water of Example 1 was replaced with ethanol, and B was introduced inside the silica gel-containing porous support having a partially exposed surface.
After obtaining a polypropylene cap carrying an ethanol solution of ITREX, wipe off the aqueous solution on the surface and leave it in the air dryer at 50 ± 5 ° C for 12 hours to dry the solvent and partially expose the surface. A polypropylene cap having BITREX supported on the inside of the silica gel continuous porous support was obtained.

Example 7 The ion-exchanged water of Example 1 was replaced with methanol, and B was introduced inside the silica gel-containing porous support having a partially exposed surface.
After obtaining a polypropylene cap carrying a solution of ITREX in methanol, wipe off the aqueous solution on the surface and let stand for 12 hours at 50 ± 5 ° C in a blast dryer to dry the solvent and expose the surface partially. A polypropylene cap having BITREX supported on the inside of the silica gel continuous porous support was obtained.

Example 8 After replacing the ion-exchanged water of Example 1 with chloroform and obtaining a polypropylene cap in which a chloroform solution of BITREX is supported inside a silica gel communicating porous support partially exposed on the surface, , Wipe off the aqueous solution on the surface,
The solvent was dried in a blower dryer at 50 ± 5 ° C. for 12 hours to dry the solvent to obtain a polypropylene cap carrying BITREX inside the silica gel-containing porous support having a partially exposed surface.

Example 9 The ion-exchanged water of Example 1 was replaced with butanol, and B was introduced inside the silica gel-containing porous support having a partially exposed surface.
After obtaining the polypropylene cap supporting the butanol solution of ITREX, wipe off the aqueous solution on the surface and let stand for 12 hours at 50 ± 5 ° C in a blower dryer to dry the solvent and expose a part of the surface. A polypropylene cap having BITREX supported on the inside of the silica gel continuous porous support was obtained.

Example 10 After replacing the ion-exchanged water of Example 1 with isopropanol, a polypropylene cap having a BITREX isopropanol solution supported inside a silica gel communicating porous support partially exposed on the surface was obtained. Made of polypropylene with BITREX loaded inside the silica gel communicating porous support with a part of the surface exposed by wiping off the aqueous solution on the surface and leaving it for 12 hours at 50 ± 5 ° C in a blower dryer to dry the solvent. I got a cap.

Example 11 The ion-exchanged water of Example 1 was replaced with acetone, and BI was placed inside the silica gel-containing porous support having a part exposed on the surface.
After obtaining a polypropylene cap carrying an acetone solution of TREX, the surface aqueous solution is wiped off, and the solvent is dried by leaving it at 50 ± 5 ° C. for 12 hours in a blower type dryer to expose a part of the surface. A polypropylene cap having BITREX supported on the inside of the silica gel continuous porous support was obtained.

Example 12 The ion-exchanged water of Example 1 was replaced with methyl ethyl ketone,
After obtaining a polypropylene cap carrying a BITREX methylethylketone solution inside a silica gel communicating porous support part of which is exposed on the surface, the surface aqueous solution is wiped off, and 50 ± 5 ° C. in a blower dryer. After leaving for 12 hours, the solvent was dried to obtain a polypropylene cap having BITREX supported inside the silica gel communicating porous support having a part exposed on the surface.

Example 13 The ion-exchanged water of Example 1 was replaced with benzene, and BI was introduced inside the silica gel communicating porous support having a part exposed on the surface.
After obtaining a polypropylene cap carrying a TREX benzene solution, the aqueous solution on the surface is wiped off, and the solvent is dried by leaving it in a blast dryer at 50 ± 5 ° C for 12 hours to expose a part of the surface. A polypropylene cap having BITREX supported on the inside of the silica gel continuous porous support was obtained.

Example 14 The ion-exchanged water of Example 1 was replaced with toluene, and BI was placed inside the silica gel communicating porous support partially exposed on the surface.
After obtaining a polypropylene cap carrying a TREX toluene solution, the surface aqueous solution was wiped off, and the solvent was dried by leaving it in a blower dryer at 50 ± 5 ° C for 12 hours to partially expose the surface. A polypropylene cap having BITREX supported on the inside of the silica gel communicating porous support was obtained.

Example 15 The same as Example 6 except that the silica gel continuous porous carrier of Example 6 was replaced with Radeolite F (diatomaceous earth continuous porous carrier, average particle size 10 μm, manufactured by Tsuchiya Kaolin Industry Co., Ltd.). Then, a polypropylene cap having BITREX supported on the inside of the silica gel communicating porous support having a part exposed on the surface was obtained.

Example 16 The silica gel-containing porous support of Example 6 was replaced with a glass-containing porous support (average particle diameter 5 μm, Koa Glass Industry Co., Ltd.).
Manufactured in the same manner as in Example 6, except that a part of the surface of the silica gel communicating porous support is exposed to BI.
A polypropylene cap carrying TREX was obtained.

Example 17 The same procedure as in Example 6 was repeated except that the silica gel communicating porous support of Example 6 was replaced by a zeolite communicating porous support, having an average particle size of 5 μm, manufactured by Sieglite Chemical Mining Co., Ltd. ,
A polypropylene cap having BITREX supported on the inside of the silica gel communicating porous support having a part exposed on the surface was obtained.

Example 18 The same as Example 6 except that the silica gel continuous porous carrier of Example 6 was replaced with BELLFINE D-10 (cellulose continuous porous carrier, average particle size 7 μm, manufactured by Kanebo Co., Ltd.). In the same manner, a polypropylene cap having BITREX supported on the inside of the silica-gel communicating porous support having a part exposed on the surface was obtained.

Example 19 The silica gel continuous porous carrier of Example 6 was prepared using Aqua Reserve AP (high-grade water-soluble resin, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
In the same manner as in Example 6 except that the BITR was added to the inside of the silica gel communicating porous support having a partially exposed surface.
A polypropylene cap carrying EX was obtained.

Example 20 The silica gel continuous porous carrier used in Example 1 was prepared by dissolving 50 ppm of BITREX in ion-exchanged water.
After mixing with an aqueous solution of ± 2 ° C, the water is removed by filtration, and the mixture is left for 12 hours at 50 ± 5 ° C in a blast dryer to dry the residual water, and the silica gel continuous porous carrier powder carrying BITREX is dried. Got An ink for screen printing was obtained with the following formulation. BITREX-supported silica gel continuous porous carrier powder 10 parts Printex 30 (carbon black, manufactured by Tegusa) 20 parts Calcium carbonate 15 parts Haliphenol 553 (rosin-modified phenol resin, manufactured by Harima Chemicals Co., Ltd.) 20 parts Soft Bent Naphtha No. 1 35 parts As an ink formulation, firstly Hariphenol 553 was added to Soft Bent Naphtha No. 1 and stirred for 1 hour to dissolve, then Printex 30 and calcium carbonate were added, and the mixture was mixed with a three-roll mill to give 5 I went around. BITRE to this
Silica gel continuous porous carrier powder carrying X was added and stirred for 1 hour to obtain a screen printing ink.

A polyester plate (80 mesh) was used for the screen plate, and the emulsion thickness was 30 μm.
The pattern was a circle with a diameter of 1 mm, and the pattern interval was 1 mm on the left and right. The ink used is a mixture of the above-mentioned screen plate and a dedicated curing agent, and the shaft is rotated to form an uneven pattern.
Formed. After the formation, the cap was dried at 80 ° C. for 40 minutes to obtain a cap having an uneven pattern as shown in FIG. The state on the surface 3 of the molded article of the communicating porous carrier 4 is shown in FIG.
2 is an enlarged cross-sectional view (schematic diagram) of the I portion of the outer wall surface of the cap of FIG.

Comparative Example 1 A cap for a writing instrument was obtained in the same manner as in Example 1 except that BITREX was omitted from the cap of Example 1.

Comparative Example 2 A cap having the same shape as that of Example 1 was molded using the same material without adding a silica-gel communicating porous support, and then BITREX was dissolved in ion-exchanged water at a concentration of 50 ± 80 ± 80. The cap is dipped in an aqueous solution at 2 ° C., treated for 15 minutes while stirring so that the liquid and the entire cap come into contact with each other, taken out of the aqueous solution, and the aqueous solution on the surface is wiped off. A polypropylene cap having the BITREX aqueous solution applied to the surface is removed. Obtained.

Comparative Example 3 A cap having the same shape as that of Example 1 was molded with the same material without adding a silica gel communicating porous support, and then BITREX was dissolved in ion exchange water at a concentration of 50 ± 80 ± 80. The cap is immersed in a 2 ° C. aqueous solution, and treated for 15 minutes while stirring so that the liquid and the entire cap come into contact with each other.
A polypropylene cap having the surface thereof coated with the BITREX aqueous solution was obtained.

[0034]

EFFECT OF THE INVENTION The caps obtained in Examples 1 to 19 and Comparative Examples 1 to 3 described above were evaluated by conducting a bitterness sensing test and a transfer test of a bitterness emetic to a hand. Shown in.

Bitterness Sensitivity Test The overall sensory evaluation of the bitterness when the cap was contained in the mouth and the time until the bitterness was felt was evaluated on a scale of five.
(1: don't feel bitterness, 3: feel bitterness in about 2 seconds,
5: Immediately feel strong bitterness)

Transferability Test The surface of the cap was lightly rubbed 5 times with the index finger, and the finger was licked to determine whether the bitterness was transferred from the cap to the finger. ◎: No bitterness is felt ○: Little bitterness is felt △: Bitterness is felt ×: Strong bitterness is felt

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

As described above, when the resin molded product of the present invention is contained in the mouth, it does not clog the throat because it has an emetic action and is discharged to the outside of the mouth.

[Brief description of drawings]

FIG. 1 is a perspective view showing an embodiment.

FIG. 2 is an enlarged sectional view of a portion I in FIG.

[Explanation of symbols]

 1 Cap for Writing Instruments 2 Outer Wall 3 Outer Wall Surface 4 Communication Porous Carrier 5 Printing Surface

Claims (2)

[Claims] 1. A synthetic resin molded article obtained by supporting an emetic agent on the communication porosity of a communication porous carrier and arranging the communication porous carrier carrying the emetic agent on the surface. 2. A synthetic resin molded article is molded by adding the communicating porous carrier to a synthetic resin molding material, and then the communicating porous carrier exposed on the surface of the molded synthetic resin molded article, A method for producing a synthetic resin molded article, which carries an aqueous solution in which the emetic agent is dissolved.