JP3011410B2 - Vinyl chloride resin clay - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention can be used as a clay as a handicraft material, and can be easily erased by heating the clay (hereinafter, erased clay). More specifically, the present invention relates to an eraser clay in which the production process is easy and simplified, kneading is easy, the shape retention is good, and the eraseability after heating is high.

[Conventional technology and problems]

As this kind of technology, Japanese Patent Publication No. 47-51108 discloses 10 to 20% by weight of a vinyl chloride paste resin, 10 to 25% by weight of a phthalate ester plasticizer, and 10 to 25% by weight of a filler such as calcium carbonate.
There has been proposed a plastic material which can be used as a character eraser comprising 60% by weight and 20 to 45% by weight of a semi-gelled soft vinyl chloride product.

However, in the case of the above-mentioned plastic material, it takes complicated labor to prepare and mix a semi-gelled soft vinyl chloride product, and the production efficiency is poor. Oil absorption, the gelability and the degree of gelation of semi-gelled soft vinyl chloride resin must be taken into account, and it is extremely difficult to obtain products of the same quality with good reproducibility.
It involves many problems in quality control. Furthermore, since it contains a large amount of filler, there is a problem in erasing property, and for example, it is impossible to obtain a transparent erasing clay.

Japanese Patent Publication No. 47-11660 describes a vinyl chloride resin-based clay obtained by blending a plasticizer, a filler and the like with a vinyl chloride resin.

However, clay using only a plasticizer having a low gelling rate requires setting the temperature of the heat kneading to a high temperature (for example, 150 ° C. or higher). In addition, heating with boiling water is difficult, heating with boiling water takes a long time, and boiling water may evaporate during heating.

On the other hand, when a vinyl chloride resin composition using a plasticizer having a high gelation rate is heated to produce a plastigel clay, even if the temperature and time are very severely controlled, the current general heating apparatus cannot be used. Clay of a constant quality cannot be obtained with control at ± 1 ° C., and the clay may be cured and hardened in stock due to its high gelling property. In general, a plasticizer with a high gelation rate has a high migration property to other plastics, and therefore, even if, for example, clay is shaped into a certain shape and used as an ornament, the plasticizer bleeds and contaminates. There's a problem. Also, some plasticizers have a high gelation rate and low migration, but such plasticizers are expensive.

That is, by adding a plasticizer to a vinyl chloride resin and adjusting the gelation rate to a suitable level as a clay, it is not always necessary to provide an erased clay that is easily kneaded, has excellent shape retention, and is easily erased by heating. It is not easy.

[Means for solving the problem]

In view of such circumstances, the present inventors have made intensive studies to solve the above-mentioned problems, and have reached the present invention.

That is, the present invention provides a composition containing, as a main component, two or more plasticizers (excluding polyethylene glycol) having different gelling rates from a vinyl chloride paste resin, at 70 to 100 ° C.
A vinyl chloride resin-based clay which can be used as a clay for handicraft materials by heating and kneading so as to satisfy the following formula, and which can be erased by heating.

3000logx-2000 ≧ y ≧ 200, where x ≦ 60, y ≦ 1000 x: Heat-kneading time (min) y: Apparent viscosity (poise) Generally, high plasticity of vinyl chloride paste resin such as vinyl clay or erased clay The agent-containing plastic gel contains a gelling agent and a large amount of filler. Because of this gelling agent and a large amount of filler, plastigel becomes thixotropic and becomes hard and gradually soft when kneading clay, but is very hard when kneading first to maintain a predetermined shape. Need to be clay. Particularly in the case of erased clay, the necessity is great.

In addition, a method of heating a vinyl chloride paste sol and gently gelling it to obtain a plastigel is extremely difficult to apply heat history uniformly, reproducibility, and control.

The present inventors have conducted intensive studies under such circumstances, and as a result of using a plasticizer having a high gelling rate and a plasticizer having a low gelling rate in combination, a specific relationship between the heating kneading time and the apparent viscosity. It has been found that a composition that satisfies the formula provides an eraser clay that is easy to knead, has excellent shape retention properties, and has a high erasure property when heated to erase.

The plasticizer used in the present invention is not particularly limited as long as it is used in the field of eraser. For example, as a phthalate ester, dibutyl phthalate (DB
P), diheptyl phthalate (DHP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DIN
P), dinonyl phthalate (DNP), diisodecyl phthalate (DIDP), diisooctyl phthalate (DIOP), dicapryl phthalate (DCP), diundecyl phthalate (DUP), ditridecyl phthalate (DTDP), butyl benzyl phthalate ( BBP), octylbenzyl phthalate (OBP), butyloctyl phthalate (BOP), dicyclohexyl phthalate (D
CHP) and the like, and examples of the aromatic carboxylic acid esters other than the phthalic acid esters include di-2-ethylhexyl trimellitate (TOTM), diisooctyl trimellitate (TITM), and tetra-2-pyromellitic acid Methylpentyl (TXP), tetra-2-ethylhexyl pyromellitic acid (TOP) and the like, and examples of the aliphatic dibasic ester system include di-2-ethylhexyl adipate (DOA), diisodecyl adipate (DIDA), Dinonyl adipate (DNA), diisononyl adipate (DIN
A), di-2-ethylhexyl azelate (DOZ), dibutyl sebacate (DBS), di-2-ethylhexyl sebacate (DOS), and the like. Further, as a polyester type, polypropylene adipate (molecular weight 600 to 800)
0), polypropylene sebacate (molecular weight 8000), polypropylene phthalate (molecular weight 1000-3000) and the like. However, polyethylene glycol is not included in the plasticizer of the present invention because it is used as a lubricant in the field of erase and is not used as a plasticizer. Furthermore, examples of the chlorine-containing system include chlorinated paraffin (Cl40%) and chlorinated paraffin (Cl45%). In the present invention, when trying to obtain an eraser clay having excellent transparency, BBP, O
BP, and combinations of these with chlorinated paraffin.

The preferred composition of the eradicated clay of the present invention comprises 80 to 200 parts by weight of a plasticizer, 1 to 3 parts by weight of a stabilizer and 0 to 200 parts by weight of a filler based on 100 parts by weight of a vinyl chloride paste resin. If the amount of the plasticizer is less than 80 parts by weight, the erasability becomes poor, and sufficient kneadability as clay cannot be obtained. If the amount exceeds 200 parts by weight, stickiness and sufficient shape retention cannot be obtained. When the amount of the stabilizer is less than 1 part by weight or more than 3 parts by weight, the effect of adding the stabilizer becomes insufficient. When the amount of the filler exceeds 200 parts by weight, the thixotropic property becomes remarkable, and the mixture is hard at the beginning of kneading, becomes too soft as kneaded, and the erasure is deteriorated. In the present invention, in addition to the above, if necessary, flavors, coloring agents (pigments, dyes, etc.), gelling agents (calcium silicate, silica aerogel, aluminum stearate,
Organic bentonite).

In the present invention, as the plasticizer in the composition, a plasticizer having a high gelation rate and a plasticizer having a low gelation rate are used in combination. The gelation rate of the plasticizer depends on the temperature of the heat-kneading of the composition. As shown in FIG. 1, the composition containing the plasticizer has the following formula: 3000 logx−2000 ≧ y ≧ 200, where x is the heat-kneading time (minutes). Y: A plasticizer is added to satisfy the apparent viscosity (poise). Only within the range satisfying the above equation (A in the figure), eraser clay of uniform quality can be obtained under mild and easy production conditions. In the range of B in the figure, the clay is in the sol state and good clay cannot be obtained, and in the range of C, only hard and brittle clay can be obtained or clay of uniform quality cannot be obtained (for example, the heating and kneading time). Ten
Different seconds, the hardness of the clay varies greatly).

Incidentally, the apparent viscosity varies depending on the temperature. In the present invention, regardless of the temperature, in other words, at a desired temperature, a plasticizer is selected so as to satisfy the above formula, and a composition containing the same is selected. This indicates that preparation is required.

The vinyl chloride paste resin used in the present invention is not particularly limited, and all known resins can be used, for example, “PSH-10”, “PSH-650A”, and “PB-10” manufactured by Kanegafuchi Chemical Industry Co., Ltd.
M-B3 "," 121 "manufactured by Zeon Corporation, and" P-400 "manufactured by Mitsubishi Kasei Vinyl Industry Co., Ltd. still,
In the present invention, the amount of about 30% by weight or less may be replaced with ordinary vinyl chloride resin.

As the stabilizer used in the present invention, non-toxic stabilizers are preferable. For example, calcium stearate, zinc stearate, di-n-octyltin bis (isooctylthioglycolate) salt, di-n-octyltin malate Polymers, epoxidized soybean oil, tris (nonylphenyl) phosphite and the like.

Examples of the filler used in the present invention include carbonates such as calcium carbonate, silica, clay, talc, glass powder, glass beads, silicates such as silica sand, and metal hydrates such as aluminum hydroxide. . In the present invention, in order to obtain an eraser clay having excellent transparency, a transparent filler such as glass powder or glass beads is used.

In order to produce an eraser clay from the above composition, the composition is usually heated and kneaded at 70 to 100 ° C. in a mixer or kneader, and then molded into an arbitrary shape by extrusion molding, injection molding, compression molding, or the like. .

When the above-mentioned clay is erased, it is heated and hardened with hot water or an oven toaster and then cooled.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to experimental examples, but the present invention is not limited thereto. In the following experimental examples, those within the scope of the present invention are referred to as examples, and those outside the scope of the present invention are referred to as comparative examples.

Experimental Example 1 (Comparative Example) PVC paste resin 100 parts by weight (PSH-10, manufactured by Kanegabuchi Chemical Industry Co., Ltd.) DNP 100 parts by weight Calcium carbonate 60 parts by weight Zinc stearate 1 part by weight Calcium stearate 1 part by weight Epoxidized Soybean oil 3 parts by weight Put the above mixture in a 500 ml beaker, mix evenly with a homomixer, adjust the plastisol, and add
The mixture was placed in an oil bath set at 0 ° C, heated for 60 minutes while stirring the plastisol, and cooled. The obtained product did not become a gel like clay but a sol.

Experimental Example 2 (Example) PVC paste resin (PSH-10) 100 parts by weight DNP 75 parts by weight OBP 25 parts by weight Calcium carbonate 60 parts by weight Zinc stearate 1 part by weight Calcium stearate 1 part by weight Epoxidized soybean oil 3 parts by weight The mixture was placed in a 500 ml beaker, mixed homogeneously with a homomixer, and adjusted for plastisol.
The sample heated in an oil bath set at 0 ° C and heated for 10 minutes and 30 minutes while stirring the plastisol was cooled to obtain two types of eraser clay.

Experimental Example 3 (Comparative Example) PVC paste resin (PSH-10) 100 parts by weight DNP 50 parts by weight OBP 50 parts by weight Calcium carbonate 60 parts by weight Zinc stearate 1 part by weight Calcium stearate 1 part by weight Epoxidized soybean oil 3 parts by weight The mixture was placed in a 500 ml beaker, mixed homogeneously with a homomixer, and adjusted for plastisol.
The mixture was placed in an oil bath set at 0 ° C, heated for 5 minutes, 6 minutes, and 7 minutes while stirring the plastisol, and then cooled.
The sample heated for 5 minutes was a plastisol, and the sample heated for 7 minutes was very hard and brittle. The sample heated for 6 minutes was an eraser clay that was easy to knead and had excellent shape retention ability, but the gelation rate was high, so that a sample of uniform quality could not be obtained with good reproducibility.

Experimental Example 4 (Comparative Example) PVC paste resin (PSH-10) 100 parts by weight DNP 25 parts by weight OBP 75 parts by weight Calcium carbonate 60 parts by weight Zinc stearate 1 part by weight Calcium stearate 1 part by weight Epoxidized soybean oil 3 parts by weight The mixture was placed in a 500 ml beaker, mixed homogeneously with a homomixer, and adjusted for plastisol.
The mixture was placed in an oil bath set to 0 ° C., heated for 6 minutes while stirring the plastisol, and then cooled. However, it did not become a gel like clay but was hard and brittle.

Experimental Example 5 (Example) PVC paste resin (PSH-10) 100 parts by weight DINP 95 parts by weight DCHP 5 parts by weight Calcium carbonate 60 parts by weight Zinc stearate 1 part by weight Calcium stearate 1 part by weight Epoxidized soybean oil 3 parts by weight The mixture was placed in a 500 ml beaker, mixed homogeneously with a homomixer, and adjusted for plastisol.
The sample heated in an oil bath set at 0 ° C and heated for 10 minutes and 30 minutes while stirring the plastisol was cooled to obtain two types of eraser clay.

Experimental Example 6 (Example) PVC paste resin (PSH-10) 100 parts by weight DINP 90 parts by weight DCHP 10 parts by weight Calcium carbonate 60 parts by weight Zinc stearate 1 part by weight Calcium stearate 1 part by weight Epoxidized soybean oil 3 parts by weight The mixture was placed in a 500 ml beaker, mixed homogeneously with a homomixer, and adjusted for plastisol.
The sample heated in the oil bath set at 0 ° C and heated for 6 minutes and 10 minutes while stirring the plastisol was cooled to obtain two types of eraser clay.

Experimental Example 7 (Comparative Example) PVC paste resin (PSH-10) 100 parts by weight DINP 85 parts by weight DCHP 15 parts by weight Calcium carbonate 60 parts by weight Zinc stearate 1 part by weight Calcium stearate 1 part by weight Epoxidized soybean oil 3 parts by weight The mixture was placed in a 500 ml beaker, mixed homogeneously with a homomixer, and adjusted for plastisol.
After heating for 6 minutes while stirring the plastisol in an oil bath set to ° C., it was cooled, but was hard and brittle. The sample heated and cooled for 5 minutes was a plastisol, and did not become a gel-like clay.

Experimental Example 8 (Example) PVC paste resin (121, manufactured by Nippon Zeon Co., Ltd.) 80 parts by weight PVC (PBM-B3, manufactured by Kanegabuchi Chemical Industry Co., Ltd.) 20 parts by weight DOP 60 parts by weight DBP 50 parts by weight Carbonic acid Calcium 80 parts by weight Aerosil R972 2 parts by weight Zinc stearate 1 part by weight Calcium stearate 1 part by weight Epoxidized soybean oil 3 parts by weight The above composition is heated and mixed at 90 ° C. for 35 minutes using a kneader, and then mixed with a silicone female mold. After casting, cooling and demolding, erased clay was obtained.

Experimental Example 9 (Example) PVC paste resin (PSH-10) 100 parts by weight DOP 70 parts by weight DHP 50 parts by weight Calcium carbonate 80 parts by weight Zinc stearate 1 part by weight Calcium stearate 1 part by weight Epoxidized soybean oil 3 parts by weight After mixing with a propeller-type stirrer, the mixture was put into a hopper of an extruder, and extruded by setting a cylinder temperature and a die temperature to 85 ° C. to obtain an eraser clay.

Experimental Example 10 (Example) 100 parts by weight of PVC paste (PSH-650A, manufactured by Kaneka Chemical Co., Ltd.) 30 parts by weight of BBP 50 parts by weight of OBP 20 parts by weight of chlorinated paraffin 20 parts by weight 2 parts by weight of octyltin mercaptide The mixture was heated and mixed at 75 ° C. for 45 minutes using a kneader, cooled, and extruded with an extruder to obtain a transparent eraser clay.

Experimental Example 11 (Comparative Example) PVC paste resin (PSH-10) 100 parts by weight OBP 100 parts by weight Calcium carbonate 60 parts by weight Zinc stearate 1 part by weight Calcium stearate 1 part by weight Epoxidized soybean oil 3 parts by weight Place in a 500 ml beaker, mix uniformly with a homomixer, adjust the plastisol
The mixture was heated and cooled for 5 minutes while stirring the plastisol in an oil bath set at 0 ° C. However, the plastisol did not become a gel like clay but was hard and brittle.

Table 1 shows the results of Experimental Examples 1 to 11. FIG. 2 shows the gelation rate (the relationship between the heating kneading time and the apparent viscosity) of the compositions of Experimental Examples 1 to 7 and 11. 2 in FIG.
Shows Experimental Examples 1 to 11.

For Experimental Examples 8 to 10, at the respective kneaders or extrusion temperatures, gelling rate data was collected by a method of stirring the plastisol in an oil bath as in Experimental Examples 1 to 7 and 11.

From Table 1 and FIG. 2, it can be seen that the expression 3000logx−2000 ≧
The character-erasable clays obtained in Experimental Examples 2, 5, 6, 8, 9 and 10 (all of the examples) satisfying y ≧ 200 (that is, in the region of A in FIG. 1) are easy to knead. It can be seen that the shape retention is good as eraser clay. In contrast, Experimental Example 1 (Comparative Example) using one type of plasticizer had y ≧ 20.
0 (that is, in the region B in FIG. 1), the gelation rate was too slow, the clay did not turn into a sol, and Experimental Example 3
Nos. 4, 7, and 11 (all of Comparative Examples) did not satisfy 3000 logx-2000 ≧ y (that is, in the region of C in FIG. 1), the gelation speed was too high, and the heat kneading time was slightly changed to make the clay. The hardness varies greatly, making it unsuitable as an eraser clay, and only a hard, brittle clay can be obtained.

Next, the eraser clay obtained in Experimental Examples 2, 5, 6, 8, 9, and 10 was placed in an oven toaster (about 300 ° C.) heated for 15 minutes, heated with residual heat for 15 minutes, and naturally cooled. Thereafter, the erasure rate (the method of JIS S 6050-1988) was measured. In addition, the transparency was obtained by compressing the eraser clay obtained in Experimental Examples 2, 5, 6, 8, 9 and 10 with a press to smooth the surface.
Heat for 15 minutes with the residual heat of the oven toaster as above,
Observed after natural cooling. Table 2 shows the measurement results of the erasure rate and the observation results of the transparency.

[Action and effect] As described above, clay using only a plasticizer having a low gelation rate requires setting the temperature of heating and kneading to a high temperature (for example, 150 ° C or higher), and heating at home to erase. If, for example, heating with an oven toaster is also difficult,
In addition, heating with boiling water takes a long time, and boiling water may evaporate during heating.

On the other hand, in the case of producing clay using a plasticizer having a high gelation rate alone, when heating the vinyl chloride paste resin composition to produce a plastic gel clay, the temperature and time management are made very severe. However, it is not possible to obtain clay of a constant quality by controlling the current general heating apparatus at ± 1 ° C. In addition, since the gelling property is high, the clay may be cured in stock and hardened. In general, a plasticizer with a high gelation rate has a high migration property to other plastics, and therefore, even if, for example, clay is shaped into a certain shape and used as an ornament, the plasticizer bleeds and contaminates. There's a problem. Also, some plasticizers have a high gelation rate and low migration, but such plasticizers are expensive.

That is, there is a problem that the gelation rate of the clay is too fast or too slow, and the clay can be easily produced using the plasticizer alone,
In addition, it is extremely difficult to provide an eraser clay having a balance between the performance as a clay and the performance as an eraser.

The present invention simplifies the clay production process by using a combination of a plasticizer having a high gelling rate and a plasticizer having a low gelling rate, and making the composition satisfy a specific relational expression between the heating kneading time and the apparent viscosity. It has a stable quality, little change over time of the clay, a high ability to retain the shape of the clay at normal temperature and during heating, and can be easily heated and erased by ordinary households. The resulting eraser can provide an eraser clay having excellent eraser properties.

[Brief description of the drawings]

FIG. 1 is a view showing a preferred range of the gelation rate of the composition used in the present invention, and FIG. 2 is a view showing the gelation rate of the composition used in the experimental examples of the present invention.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yasuhiro Nishioka 6-11-3 Takaden, Asahi-ku, Osaka-shi, Osaka (56) References JP-A-59-24737 (JP, A) JP-B-47-11660 ( JP, B1)

Claims (2)

(57) [Claims] 1. A composition containing as a main component two or more plasticizers (excluding polyethylene glycol) having different gelation rates from a vinyl chloride paste resin, at 70 to 100 ° C., satisfying the following formula: A vinyl chloride resin-based clay that can be used as a clay for handicraft materials, and can be erased by heating. 3000logx-2000 ≧ y ≧ 200, where x ≦ 60, y ≦ 1000 x: Heat-kneading time (min) y: Apparent viscosity (poise) 2. The composition according to claim 1, wherein 80 to 200 parts by weight of a plasticizer, 1 to 3 parts by weight of a stabilizer and 0 to 200 parts by weight of a filler are blended with 100 parts by weight of the vinyl chloride paste resin. Clay.