JP7066146B2 - Clay for work - Google Patents

Description

The present invention relates to clay for work used in kindergartens, nursery schools, elementary schools and the like. Specifically, it does not freeze even in a low temperature environment such as in a freezer, it is softened to the extent that it can be shaped by heating it by holding it by hand, it is not sticky, it has a silky feel, it has extensibility, and it has the desired shape. It has excellent characteristics that it can be shaped well, the shaped shape can be maintained in a room temperature environment, and then it is softened to the extent that it can be shaped by reheating to the extent that it can be held by hand and warmed, and then it can be shaped again. Regarding clay.

In kindergartens, nursery centers, elementary schools, etc., clays having characteristics such as smooth texture, non-greasyness, and easy modeling are desired as clays used as teaching materials for arts and crafts.
For example, Japanese Patent Application Laid-Open No. 2004-102163 (Patent Document 1) states that it is harmless even if it is accidentally put into the mouth, has no odor, and is non-adhesive to the hand, extensibility, shape retention, workability, and modeling. A clay composition having excellent properties is disclosed.
Further, Japanese Patent Application Laid-Open No. 10-020768 (Patent Document 2) has appropriate hardness and stretchability, and also has moderate brittleness and other creativity, and is long after drying. Lightweight clays that can maintain robustness for a period of time have been disclosed.

Japanese Unexamined Patent Publication No. 2004-102163 Japanese Unexamined Patent Publication No. 10-020768

Clays with excellent properties are desired. For example, a clay having characteristics such as non-greasy, silky feel, extensibility, good shaping of a desired shape, and retention of shape for a long period of time after molding is desired. There is.

INDUSTRIAL APPLICABILITY The present invention does not freeze even in a low temperature environment such as in a freezer, is softened to the extent that it can be shaped by heating to the extent that it can be held and warmed by hand, is not sticky, has a silky feel, has extensibility, and has a desired shape. Clay with the characteristics that it is easy to form, the formed shape can be maintained in a room temperature environment, and then it is softened to the extent that it can be formed by reheating to the extent that it can be held by hand and warmed, and then it can be formed again. The purpose is to provide.

The present invention can be described as the following [1A], [2] to [5] .
[1] Configuration 1
It is made by kneading aggregate, a first adhesive, a second adhesive, calcium chloride, an adhesive inhibitor, and water.
The aggregate contains talc and
The first adhesive contains one or more selected from CMC, methylcellulose, cornstarch, mannan powder, and polysaccharides.
The pressure-sensitive adhesive component contains one or more selected from silicone oil, glycerin, propylene glycol, and sodium hyaluronate.
The viscosity for work is characterized by that.
[1A] Configuration 1A
It is made by kneading aggregate, a first adhesive, a second adhesive, calcium chloride, an adhesive inhibitor, and water.
The aggregate contains talc and
The first adhesive contains one or more selected from CMC, methylcellulose, cornstarch, mannan powder, and polysaccharides.
The pressure-sensitive adhesive component contains one or more selected from silicone oil, glycerin, propylene glycol, and sodium hyaluronate .
The aggregate is 12 to 36% by mass, the first sizing agent is 4 to 12% by mass, the second sizing agent is calcium chloride is 9 to 27% by mass, and the adhesion suppressing component is 0.1 to 2%. By mass, the water is in the range of 40-60% by mass, for a total of 100% by mass.
Work clay characterized by that.
[2] Configuration 2
In Configuration 1A
The aggregate further comprises one or more selected from calcium sulfate, sodium sulfate, magnesium sulfate, silicon dioxide, magnesium carbonate, eggshell.
Work clay characterized by that.
The amount of talc in the entire aggregate is, for example, 60% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more when the aggregate is 100% by mass. For example, an aggregate can be composed of 20 parts by mass of talc and 4 parts by mass of calcium sulfate.
[3] Configuration 3
In Configuration 1A or Configuration 2,
The first glue (thickener) essentially contains CMC.
Work clay characterized by that.
The amount of CMC in the entire first adhesive is, for example, preferably 75% by mass or more, more preferably 85% by mass or more, when the first adhesive is 100% by mass.
[4] Configuration 4
In any of Configuration 1 A to Configuration 3,
The adhesive suppressing component (release component) indispensably contains silicone oil.
Work clay characterized by that.
The amount of the silicone oil in the entire pressure-sensitive adhesive component is, for example, preferably 80% by mass or more, more preferably 90% by mass or more, when the pressure-sensitive adhesive component is 100% by mass.
[5] Configuration 5
In configuration 4,
The silicone oil is dimethylpolysiloxane,
Work clay characterized by that.
[6] Configuration 6
In any of the configurations 1 to 5,
The aggregate is 12 to 36% by mass, the first glue is 4 to 12% by mass, the second glue, calcium chloride, is 9 to 27% by mass, and the adhesive inhibitory component is 0.1 to 2 by mass. By mass, the water is in the range of 40-60% by mass, for a total of 100% by mass.
Work clay characterized by that.
For example, 20 g of talc and 4 g of calcium sulfate as aggregate, 8 g of sodium carboxymethyl cellulose (CMC) as the first adhesive, 18 g of calcium chloride as the second adhesive, 0.5 g of dimethylpolysiloxane as an adhesive inhibitor, and It is a mixture of 49.5 g of water.

The clay of composition 1A is made by kneading an aggregate, a first adhesive, a second adhesive, calcium chloride, an adhesion suppressing component, and water, and the aggregate contains talc, and the first The adhesive of 1 contains one or more selected from CMC, methyl cellulose, corn starch, mannan powder, and polysaccharide, and the adhesive inhibitory component is one selected from silicone oil, glycerin, propylene glycol, and sodium hyaluronate. Including the above, the aggregate is 12 to 36% by mass, the first adhesive is 4 to 12% by mass, the second adhesive, calcium chloride, is 9 to 27% by mass, and the adhesive inhibitory component is Since it is a work clay characterized by 0.1 to 2% by mass and 40 to 60% by mass of the water and 100% by mass in total, it does not freeze even in a low temperature environment and can be held by hand. It is softened to the extent that it can be shaped by heating it to the extent that it can be warmed up, it is not sticky, it has a silky feel, it has good extensibility, it can shape the desired shape well, and the shaped shape is long in a room temperature environment. It can be maintained for a period of time, and after that, it can be softened to a degree that it can be molded by reheating to the extent that it can be held by hand and warmed, and it can be provided with the property that it can be molded again.

A drawing substitute photograph taken from above with each model placed side by side with a ruler (60 cm). According to the product of the present invention, in order to show that even small-sized flakes can be modeled well, a triceratops-like animal image with frills (Delmos paraokipital), which was not possible with the conventional product in small size, was modeled. A drawing substitute photograph taken from the front of each modeled object in FIG. 1 in order to make it easier to understand the shape of each modeled object. The leftmost model is not placed in FIG. 1, but was added in FIG. 2 to assist in understanding the shape.

Hereinafter, embodiments of the present invention will be described.
As the talc (hydrous magnesium silicate), for example, one having an average particle size of about 50 to 1 [μm] can be preferably used. Further, if it is provided as a food additive, it is preferable from the viewpoint of safety.

The CMC (carboxymethyl cellulose / sodium carboxymethyl cellulose) has a viscosity of 800 to 8000 [mPa · s], preferably 2000 to 7000 [mPa · s], and more preferably 2500 to 6000 [mPa · s] at a 1% aqueous solution at 25 ° C. The range of [s] can be preferably used.
For example, Daicel FineChem Co., Ltd.'s "CMC Daicel (registered trademark of the company) product numbers 2200, 2260; both are high-purity products with an etherification degree of 0.8 to 1.0" and Nippon Paper Co., Ltd.'s "Sun". Rose (SUNROSE is a registered trademark of the company), "Cerogen (registered trademark of the company) 3H, 4H, BSH-6, BSH-12, F3H, F-BSH-" manufactured by Daicel FineChem Pharmaceutical Co., Ltd. 12, F-6HS9 ”etc. are applicable or partially applicable. Further, if it is provided as a food additive, it is preferable from the viewpoint of safety. The degree of etherification is preferably in the range of 0.60 to 1.00, more preferably 0.65 to 0.95.
As the methyl cellulose, one having a viscosity equivalent to that of CMC can be preferably used. For example, a product provided by Shin-Etsu Chemical Co., Ltd. under the trade name of "Metro's (registered trademark of the same company)" and having a viscosity equivalent to that of CMC described above can be preferably used.

The silicone oil preferably has a kinematic viscosity at 25 ° C. in the range of 1 to 1000 [mm ² / s], preferably 10 to 900 [mm ² / s], and more preferably 50 to 800 [mm ² / s]. Can be used for. Further, as the silicone oil, for example, dimethylsilicone oil such as dimethylpolysiloxane can be preferably used. For example, the "KF-96" series manufactured by Shin-Etsu Chemical Co., Ltd. is applicable or partially applicable. The "KF-96ADF" series provided for food is also preferable from the viewpoint of safety.

Examples and comparative examples will be described below.
The working clays of Example (12 cases) and Comparative Example (2 cases) were prepared and their characteristics were evaluated. In addition, Example 1 is substantially composed of 6 cases. That is, it consists of 6 cases in which the viscosity of CMC and the kinematic viscosity of dimethylpolysiloxane were changed.
(1) Example 1
Aggregate-1: Talc (hydrous magnesium silicate) 20 [g]
(Product name: food additive talc S-1, average particle size 8.7 [μm])
Aggregate-2: Calcium sulfate 4 [g]
(Product name: food additive calcium sulfate, substance name: calcium sulfate dihydrate)
Adhesive: CMC 8 [g]
(Product name: Cellogen F series (for food industry), Substance name: Sodium carboxymethyl cellulose, Viscosity range at 25 ° C. in 1% aqueous solution: 3000 to 5000 [mPa · s], 3 types (about 3000, 4000, 5000) )
Calcium chloride: Calcium chloride 18 [g]
(Product name: RS (calcium chloride), substance name: calcium chloride dihydrate)
Adhesive inhibitor: Silicone oil 0.5 [g]
(Shin-Etsu Chemical Co., Ltd., product name: KF-96ADF series, substance name: dimethylpolysiloxane, kinematic viscosity at 25 ° C: 60 to 500 [mm ² / s], 4 types (about 60, 150, 350, 500) )
Water: Water 49.5 [g]
Was mixed and kneaded.
Here, the combination of the viscosity of CMC [mPa · s] and the kinematic viscosity of dimethylpolysiloxane [mm ² / s] is
(1) "3000, 60"
(2) "3000,150"
(3) "3000,350"
(4) "3000,500"
(5) "4000,150"
(6) "5000,150"
The "Example 1" cited in Examples 2 to 12 and Comparative Examples 1 and 2 described later refers to the combination of (2) "3000, 150".
The evaluation results are shown in the table together with other examples and comparative examples. The evaluation criteria are as follows.
Note (a) State when taken out after being stored in the freezer for 2 days ×: Frozen, △: Slightly frozen, ○: Not frozen (b) After taking out, hold for 2 minutes and knead Softened state ×: Not softened, △: Slightly softened, ○: Softened (c) Feeling when softened ×: Adhering to hands, △: Sticky but not adhering to hands, ○: Smooth ( d) Formability ×: Fragile and broken and cannot be modeled, Δ: It takes time but can be modeled in general, ○: Formable An animal image similar to Triceratops) with a width of about 5 mm.
In addition, when I purchased and investigated a commercially available product that claims non-adhesiveness to the hand, extensibility, etc., and further indicates that it is a patented product (the patent number is not displayed). It was not possible to form an animal image similar to Triceratops (an image having a flaky part) with a width of 3 cm or less.
(E) Extensibility (length cut when pulled by holding both ends of the lump before modeling)
X: Length ≤ 50 cm, Δ: 50 cm <Length ≤ 1 m, ◯: 1 m <Length (f) Shape retention (after the modeling in (d) above, leave it in a room temperature environment for 2 weeks)
×: Collapsed, △: Slightly collapsed, ○: Not collapsed (g) Recyclability (after modeling, seal and leave in room temperature environment for 2 weeks, remodeling possible)
×: Remodeling is not possible, △: It takes time, but remodeling is possible, ○: Remodeling is possible

The "Example 1" referred to in Examples 2 to 12 and Comparative Examples 1 and 2 below is a combination of (2) in (1) to (6) of Example 1 described above, that is,
CMC: Viscosity at 25 ° C. in 1% aqueous solution is about 3000 [mPa · s],
Dimethylpolysiloxane: kinematic viscosity at 25 ° C is about 150 [mm ² / s],
Here is an example of a combination of.

(2) Example 2 (less adhesive inhibitor)
Work clay was prepared with the same materials and formulations as in Example 1 except that "dimethylpolysiloxane", which is an adhesive suppressing component, was set to "0.2 [g]" (less).
(3) Example 3 (more adhesive inhibitor component)
Work clay was prepared with the same materials and formulations as in Example 1 except that "dimethylpolysiloxane", which is an adhesive suppressing component, was set to "1.9 [g]" (more).
(4) Example 4 (adhesion-suppressing component is considerably less)
Work clay was prepared with the same materials and formulations as in Example 1 except that "dimethylpolysiloxane", which is an adhesive suppressing component, was set to "0.05 [g]" (quite less).
(5) Example 5 (adhesion-suppressing component considerably large)
A clay for work was prepared with the same materials and formulations as in Example 1 except that "dimethylpolysiloxane", which is an adhesive suppressing component, was set to "2.1 [g]" (a considerably large amount).

(6) Example 6 (less water)
Work clay was prepared with the same materials and formulations as in Example 1 except that the water was set to "42 [g]" (less).
(7) Example 7 (more water)
Work clay was prepared with the same materials and formulations as in Example 1 except that the water was set to "58 [g]" (more).
(8) Example 8 (water is considerably less)
Work clay was prepared with the same materials and formulations as in Example 1 except that the water was set to "35 [g]" (quite less).
(9) Example 9 (quite a lot of water)
Work clay was prepared with the same materials and formulations as in Example 1 except that the water was set to "65 [g]" (quite large).
(10) Example 10 (CMC low viscosity)
Work clay was prepared with the same materials and formulations as in Example 1 except that the viscosity of CMC was set to "1000 [mPa · s] (low viscosity).
(11) Example 11 (CMC high viscosity)
Work clay was prepared with the same materials and formulations as in Example 1 except that the viscosity of CMC was set to "6000 [mPa · s] (high viscosity).

(12) Example 12 (Didimethylpolysiloxane high viscosity)
Work clay was prepared with the same materials and formulations as in Example 1 except that the kinematic viscosity of dimethylpolysiloxane at 25 ° C. was 950 [mm ² / s].

(13) Comparative Example 1 (without calcium chloride)
It was prepared in Example 1 without using calcium chloride.
Even when I tried to knead it, it became lumpy and sticky, and it was extremely difficult to knead it, so I could not make what could be called clay for work.
(14) Comparative Example 2 (without adhesive inhibitor)
It was prepared in Example 1 without using silicone oil.
It was not a "working clay" suitable for the purpose of the present invention because it was very sticky and adhered severely to the hands.

As can be seen from Examples 1 to 3, 6 and 7, talc 12 to 36% by mass as an aggregate, CMC 4 to 12% by mass as a first adhesive, and calcium chloride 9 as a second adhesive. Sufficiently good results were obtained when ~ 27% by mass, 0.1 to 2% by mass of dimethylpolysiloxane as a release agent, and 40 to 60% by mass of water were blended to a total of 100% by mass. rice field.

As can be seen from Examples 1 and 4, when the amount of silicone oil was small, a "slight sticky feeling" occurred when the silicone oil was held by hand, but it did not adhere to the hands. Further, as can be seen from Examples 1 and 5, when a large amount of silicone oil was used, it softened when held by hand but was not rapid and did not adhere to the hands, but a slight sticky feeling was felt. occured.
It should be noted that all of Examples 4 and 5 were tentatively suitable for the object of the present invention.

As can be seen from Examples 1 and 8, when the amount of water was reduced, there were some problems in formability, extensibility, and shape retention, but for the time being, it was only suitable for the object of the present invention. rice field.
Further, as can be seen from Examples 1 and 9, when a large amount of water was used, it did not soften quickly when held by hand and did not adhere to the hand, but a slight sticky feeling occurred. In addition, there was a slight problem in extensibility. In addition, all of them were tentatively suitable for the object of the present invention.

As can be seen from Examples 1 and 10, when the viscosity of CMC was set to low viscosity, it did not adhere to the hand, but a slight sticky feeling occurred. In addition, there are some problems in formability and shape retention. Further, as can be seen from Examples 1 and 11, when the viscosity of CMC was set to high viscosity, it did not adhere to the hand, but a slight sticky feeling occurred. In addition, there were some problems in formability and extensibility. In addition, all of Examples 10 and 11 were tentatively suitable for the object of the present invention.

Further, as can be seen from Examples 1 and 12, when the kinematic viscosity of the silicone oil was set to high viscosity, a slight sticky feeling occurred, but it did not adhere to the hand, and for the time being, it was the object of the present invention. It was suitable.

As can be seen from Comparative Example 1, in the case of lacking calcium chloride, it was not possible to produce what could be called working clay in the first place, without comparing with Examples.
Further, as can be seen from Comparative Example 2, when the silicone oil was lacking, clay could be produced, but it could not be said to be a working clay suitable for the object of the present invention.

In addition, instead of CMC and / or using one or more of cornstarch, methylcellulose, mannan powder, and polysaccharide together with CMC, Examples 1 (Examples 2 to 12 and Comparative Examples 1 and 2) were cited. Good results were also obtained when blended in the same manner as in 1).
Similarly, in Example 1 (Examples 2 to 12, Comparative Examples 1 to 2) using one or more of sodium hyaluronate, glycerin, and propylene glycol in place of dimethylpolysiloxane and / or together with dimethylpolysiloxane. Good results were also obtained when blended in the same manner as in Example 1 cited).
Further, by blending calcium chloride, a clay suitable for the object of the present invention was obtained, and an antiseptic effect and an antifungal effect were obtained.
In addition, although not shown in the evaluation in the table, good results were obtained in terms of peelability, curability, softening prevention, and adhesion prevention by adding talc.
In addition, an antibacterial effect was obtained by blending calcium sulfate.

Further, for a sample prepared with the same composition as in Example 1 (the same as in Examples 1 cited in Examples 2 to 12 and Comparative Examples 1 and 2), a synthetic dye "trade name:" manufactured by Saneigen FFI Co., Ltd. By adding a small amount of "edible red No. 106", it was possible to color "red" without any problem.
Similarly, by adding a small amount of "trade name: Blue No. 1", it can be colored "blue" without any problem, and by adding a small amount of "trade name: Yellow No. 4, Yellow No. 5", there is no problem with "yellow". By adding a small amount of "Nippon Aim Co., Ltd., trade name: bamboo charcoal powder", it was possible to color "black" without any problem.

Claims (5)

It is made by kneading aggregate, a first adhesive, a second adhesive, calcium chloride, an adhesive inhibitor, and water.
The aggregate contains talc and
The first adhesive contains one or more selected from CMC, methylcellulose, cornstarch, mannan powder, and polysaccharides.
The pressure-sensitive adhesive component contains one or more selected from silicone oil, glycerin, propylene glycol, and sodium hyaluronate.
The aggregate is 12 to 36% by mass, the first sizing agent is 4 to 12% by mass, the second sizing agent is calcium chloride is 9 to 27% by mass, and the adhesion suppressing component is 0.1 to 2%. By mass, the water is in the range of 40-60% by mass, for a total of 100% by mass.
Work clay characterized by that. In claim 1,
The aggregate further comprises one or more selected from calcium sulfate, sodium sulfate, magnesium sulfate, silicon dioxide, magnesium carbonate, eggshell .
Work clay characterized by that. In claim 1 or claim 2.
The first adhesive essentially comprises CMC,
Work clay characterized by that. In any one of claims 1 to 3,
The anti-adhesive component essentially contains silicone oil.
Work clay characterized by that. In claim 4,
The silicone oil is dimethylpolysiloxane,
Work clay characterized by that.

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