JP4353553B2 - Shrinkage indicator - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a shrinkage indicator composed of porous particles made of a hydrophilic resin.
[0002]
[Prior art]
In general, a gel-like material impregnated with water and a substance having a deodorizing effect is used as a deodorant. In this deodorant, the gelled material shrinks as the impregnated water or the like is volatilized, so that the end of volatilization can be visually confirmed.
[0003]
[Problems to be solved by the invention]
However, when the volatilization ends, the contracted gel-like material adheres to the wall surface of the container. Therefore, when the gel-like material is refilled, it is difficult to remove the gel-like material and the container is difficult to reuse. Furthermore, at the end of volatilization, the contracted gel-like material adheres to the wall surface of the container, so that the appearance at the end of volatilization is not good.
[0004]
In addition, since the gel-like material does not easily hold the water or deodorant substance, the water or deodorant substance exudes from the gel-like substance during transportation or use, so-called water separation. There is a case.
[0005]
Therefore, the present invention is intended to obtain a shrinkage indicator that is difficult to separate from water and that is difficult to adhere to a wall surface or the like.
[0006]
[Means for Solving the Problems]
In order to solve the above problems, the present invention comprises a porous particle group made of a hydrophilic resin, and the porous particle group is impregnated with an aqueous volatile liquid containing at least water or alcohol. The ratio B / A between the apparent volume A of the particle group and the apparent volume B of the porous particle group when the water-based volatile liquid is volatilized is set to 1/3 or less.
[0007]
The hydrophilic resin can be a resin containing at least cellulose or a cellulose derivative. Further, when the volume of the hydrophilic resin porous particles impregnated with the water-based volatile liquid is C, and the volume occupied by the hydrophilic resin is D, (C−D) / C Can be set to 0.3 to 0.98.
[0008]
Since porous particles are used, there is little adhesiveness and adhesion to a wall surface is prevented after use. For this reason, refilling of particles becomes easy.
[0009]
In addition, since the porous particles made of a hydrophilic resin have a high affinity with water, the water retainability is high, and water or the like oozes out from the porous particles during transportation or use, that is, the water is separated. To prevent.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
[0011]
First, the shrinkage indicator is an indicator in which the contents are greatly shrunk before and after use, and the replacement time of the product after use can be easily determined from the degree of shrinkage.
[0012]
The shrinkage indicator according to the present invention is composed of a porous particle group made of hydrophilic resin, and the shrinkage of the porous particle itself occurs along with the volatilization of the water-based volatile liquid, and the volatilization state is the size of the particle itself. Shown by change.
[0013]
The hydrophilic resin refers to a resin having water affinity, and examples thereof include cellulose derivatives such as cellulose, carboxymethyl cellulose and cellulose acetate, chitin, chitosan, polyvinyl alcohol, and hydrophilic polyurethane. A product obtained by molding this hydrophilic resin into porous particles has a high water affinity, and therefore has a high ability to retain water and the like, and can prevent water and the like from seeping out. In particular, when cellulose or a cellulose derivative is used, the effect is remarkable. Moreover, since there is little adhesiveness, it can prevent adhering to a wall surface etc.
[0014]
The porous particles are impregnated with a water-based volatile liquid. This water-based volatile liquid is a volatile liquid containing at least alcohol such as water or methanol or ethanol, and can contain a volatile substance having deodorizing ability.
[0015]
The amount of the water-based volatile liquid impregnated in the porous particles is preferably a water-based volatile liquid / porous particle group (dried body) of 2 times or more in weight ratio, and preferably 3 to 9 times.
[0016]
When the porous particles impregnated with the water-based volatile liquid are left in the air, the water-based volatile liquid is vaporized. After volatilization, the amount of the water-based volatile liquid impregnated in the porous particles is preferably 1/5 or less in weight ratio of water-based volatile liquid / porous particles (dried body). It is preferable to be 1/20 times.
[0017]
When the porous particles impregnated with the water-based volatile liquid are left in the atmosphere, the water-based volatile liquid is volatilized, but the porous particles shrink simultaneously with the volatilization. For this reason, it becomes possible to judge the completion | finish of volatilization of a water-based volatile liquid visually.
[0018]
The apparent volume of the porous particle group in a state where the porous particle is impregnated with the aqueous volatile liquid is A, and the apparent volume of the porous particle group when the aqueous volatile liquid is volatilized is B. In this case, the ratio B / A is preferably 1/3 or less, and preferably 1/5 to 1/20. If this ratio is larger than 1/3, it is likely to be difficult to discriminate at the end of volatilization.
[0019]
Further, as the characteristics of the hydrophilic resin-made porous particles themselves, the volume of the particles when the hydrophilic resin-made porous particles are impregnated with the water-based volatile liquid is C, and the hydrophilic resin occupies the volume. When the volume is D, the value of (C−D) / C is preferably 0.3 to 0.98, and more preferably 0.7 to 0.95. If it is less than 0.3, the reduction rate of the porous particles due to volatilization becomes small, and discrimination at the end of volatilization tends to be difficult. Moreover, when larger than 0.98, the intensity | strength of porous particle itself may fall and particle | grains may collapse | crumble and an external appearance may worsen.
[0020]
The porous particles are produced by various methods. For example, the porous cellulose particles can be produced by the following method.
[0021]
A porous agent such as calcium carbonate is added to a viscose solution having a cellulose concentration of 7% or less, and the resultant is dropped into a coagulant such as an acid solution or a coagulation / regeneration agent in the form of droplets. After solidification or coagulation / regeneration, it is washed with water, and then immersed in a predetermined water-based volatile liquid without drying to impregnate the particles with the water-based volatile liquid. Thereby, porous cellulose particles impregnated with the water-based volatile liquid can be obtained.
[0022]
The porous particles can be used as a shrinkage indicator as follows. As shown in FIG. 1 (a), porous particles 1 a impregnated with a water-based volatile liquid are stored in a container 2. The container 2 is left in an open state. Then, as time passes, as shown in FIG. 1B, the water-based volatile liquid impregnated in the porous particles 1a is volatilized and the contracted porous particles 1b are seen.
[0023]
When a predetermined time elapses, almost all the porous particles shrink as shown in FIG. At this time, if the side surface from the bottom surface of the container 2 to a predetermined height is shielded by the black seal 3 or the like, the contracted porous particles are hidden by the black seal 3. For this reason, it can be judged that the volatilization of the water-based volatile liquid has ended.
[0024]
When a volatile substance having a deodorizing ability is included in this water-based volatile liquid, the porous particles can be used as a deodorant. Moreover, when it will be in the state shown in FIG.1 (c) by use and the said porous particle will no longer be visible from the side, it can be judged that the replacement time has come. At this time, since the contracted porous particles have no adhesiveness, they can be easily taken out from the container 2 and can be easily refilled.
[0025]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples.
[0026]
[Example 1]
18.0 g of calcium carbonate (SS # 30 manufactured by Nitto Flour Chemical Co., Ltd.) is added to 100 g of viscose for producing cellophane (cellulose concentration 6.0%), and this is dropped into 2N hydrochloric acid dropwise. Porous cellulose particles having an average particle diameter of 5 mm were produced. The volume C when the porous cellulose particles were impregnated with water was 64 ml, and the volume D occupied by cellulose in the porous cellulose particles was 3 ml. Therefore, the value of (C−D) / C was 0.95. At this time, the volume C and the volume D were measured as follows. That is, 100 ml of water was put into a 200 ml graduated cylinder, and porous cellulose particles impregnated with water were put. The volume increased at this time was defined as C. Further, the porous cellulose particles were absolutely dried and the weight was measured. And the volume D was computed from the following formula.
[0027]
Volume D = absolute dry weight of cellulose among porous cellulose particles / specific gravity of cellulose A part of the above particles are lifted from hydrochloric acid, washed with water, and 65 g of particles that are impregnated with water (apparent volume 100 ml). As shown in FIG. 1 (a), it was put into a cylindrical glass container (diameter 3.8 cm, height 10 cm, and the side surface of the container is black sealed from the bottom to 3 cm in height). The upper surface was left in a room temperature of 20 ° C. with a lid having a vent hole.
[0028]
After 3 weeks, as shown in FIG. 1C, the particle group that had reached a height of 9 cm became a height of 2 cm, and because of the black seal, the particle group could not be seen from the side.
[0029]
In addition, water did not ooze out from the porous cellulose particles impregnated with water. The average particle diameter of the porous cellulose particles after standing was 3 mm and the apparent volume was 23 ml. Here, the apparent volume was measured by putting a group of porous cellulose particles in a graduated cylinder and tapping the bottom.
[0030]
Furthermore, no adhesiveness was observed in the contracted porous cellulose particles, and the porous cellulose particles could be easily discharged from the container.
[0031]
[Example 2]
The porous cellulose particles produced in Example 1 were washed with water and then immersed in ethanol to replace the water in the porous cellulose particles with ethanol. The porous cellulose particles impregnated with ethanol were allowed to stand for 3 weeks in the same manner as in Example 1.
[0032]
As a result, the particle group having a height of 9 cm became 2 cm in height, and because of the black seal, the particle group could not be visually observed from the side.
[0033]
In addition, ethanol did not ooze out from the porous cellulose particles impregnated with ethanol. The average particle size of the porous cellulose particles after standing was 3 mm and the apparent volume was 24 ml.
[0034]
Furthermore, no adhesiveness was observed in the contracted porous cellulose particles, and the porous cellulose particles could be easily discharged from the container.
[0035]
Example 3
Porous cellulose-PVA composite particles were obtained in the same manner as in Example 1 except that 50 g of a 10% aqueous solution of polyvinyl alcohol (PVA) was used for 100 g of viscose (cellulose concentration 6.0%) as a raw material ((C- D) /C=0.93). The following experiment was conducted in the same manner as in Example 1.
[0036]
As a result, the particle group having a height of 9 cm was 2.5 cm in height, and because of the black seal, the particle group could not be visually observed from the side.
[0037]
In addition, water did not ooze out from the porous cellulose-PVA composite particles impregnated with water. The average particle diameter of the porous cellulose-PVA composite particles after standing was 3.2 mm, and the apparent volume was 28 ml.
[0038]
Further, the porous cellulose-PVA composite particles that had shrunk were not sticky, and could be easily discharged from the container.
[0039]
[Comparative Example 1]
In the method for producing the porous cellulose particles of Example 1, non-porous water was obtained in the same manner as in Example 1 except that calcium carbonate was not added and that it was previously dried and impregnated with water. Impregnated cellulose particles were produced.
[0040]
The non-porous water-impregnated cellulose particles were put in the container described in Example 1 as they were and left in the same manner as in Example 1 for 3 weeks.
[0041]
As a result, the particle group having a height of 9 cm decreased only to a height of 7 cm, and the end of volatilization could not be identified.
[0042]
【The invention's effect】
According to the present invention, the volume greatly shrinks before and after use, the replacement time is clearly judged, and after the porous particles are used, the adhesion to the wall surface is prevented and the refilling of the particles becomes easy.
[0043]
Moreover, since the porous particles have a high affinity with water, the water retainability is high, and water and the like are prevented from oozing out from the porous particles when the container is tilted during transportation or use.
[Brief description of the drawings]
1A is a partially cutaway view showing a state in which a container is filled with porous particles according to the present invention; FIG. 1B is a partially cutaway view showing a state after a lapse of a little time from the state of FIG. c) Partial cutaway view showing a state after a predetermined time has elapsed from the state of (b).
1a, 1b Porous particle 2 Container 3 Black seal

Claims (2)

A porous agent is added to a viscose solution, dropped into a coagulation / regeneration agent in the form of droplets, and made up of coagulated / regenerated cellulose porous particles. The porous particles are dried after coagulation / regeneration. the apparent volume of the porous particles when no impregnated with aqueous volatile liquid containing at least water or an alcohol is a, and B the apparent volume of the porous particle group to volatilize the aqueous volatile liquid when these ratios B / a is, Ru der 1/20 1/3, the porous particles obtained by coagulation and regeneration, washing with water, dipped in the aqueous volatile liquid without drying A shrinkage indicator impregnated with the above water-based volatile liquid .   The shrinkage | contraction indicator of Claim 1 whose cellulose concentration of the said viscose solution is 7% or less.

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