JP4568542B2 - Mud composition and modeling method - Google Patents

Description

  The present invention relates to a modeling technique using a mud composition, and is particularly effective when applied to a modeling method capable of forming a modeled object without firing by curing in a state of being attached to the inner surface of the mold. Technology.

  Unlike the ceramics, etc., the present applicant has been able to produce a molded product that matches the mold by pouring into a gypsum mold of a desired shape and then removing the mold after curing. The material has been developed and marketed as non-heated cast mud.

For example, an unheated cast mud blended with an acrylic-modified urethane resin, plastic clay, and rock powder has been proposed (see Patent Document 1). Furthermore, a non-heated cast mud containing an acrylic urethane resin and a rock powder clay composition was also proposed (see Patent Documents 2 and 3).
JP-A-10-296713 JP 2000-44310 A JP 2000-119055 A

  As described above, the present applicant has been trying to disseminate various modeling techniques using non-heated casting slurry, but some users have reported that demolding may not be performed successfully. Obtained. It was also found that in the worst case, the molded product and the plaster mold may be damaged.

  The non-heated cast mud that has been supplied for some time has been excellent in its own way, but even if some of the cases cause problems such as the plaster mold being broken due to unreasonableness during demolding as described above. I thought it was necessary to take immediate measures.

  An object of the present invention is to enable easy demolding in a molding technique using non-heated cast mud.

  The above and other objects and novel features of the present invention will be apparent from the description of this specification and the accompanying drawings.

  Of the inventions disclosed in the present application, the outline of typical ones will be briefly described as follows.

The present invention relates to a mud composition used in a molding method for modeling by attaching to a surface such as an inner surface of a mold or an outer surface of an object and curing, and a resin emulsion of at least one of an acrylic resin and a urethane resin , characterized in that the resin emulsion of the silicon-based resin, and a molding material comprising a disilazide or clay are mixed. Such a mud composition is characterized by containing potassium titanate. Plant fibers such as pulp fibers may be included. In the slurry composition of any one of such configurations, the mixing of the resin emulsion and the modeling material is performed in a state where the modeling material is dispersed in water by an anionic surfactant. To do.

  Further, the present invention is characterized by pouring the slurry composition of any of the above configuration into a mold, curing in a state where the slurry composition is attached to the inner surface of the mold, and removing and molding after curing. This is a modeling method. When using a non-heated cast slurry having any of the above-mentioned configurations, such a slurry composition should be cured in a state of being adhered to the outer surface of a modeled object formed of a flexible material such as paper or cloth. It can also be shaped.

  Among the inventions disclosed in the present application, effects obtained by typical ones will be briefly described as follows.

  By using the non-heated cast slurry composition of the present invention, it has become possible to easily remove the mold from the gypsum mold even if the mold could not be removed from the gypsum mold conventionally. There is no damage.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  In the present embodiment, for example, a thin object is produced by making a thin copy on the inner surface of the mold, curing it in that state, and removing the mold to accurately reproduce the unevenness of the inner surface of the mold on the outer surface. The mud composition which can be used effectively for the modeling method to perform is demonstrated.

  In the slurry composition according to the present invention, a resin emulsion of at least one of an acrylic resin or a urethane resin, a resin emulsion of a silicon resin, and a modeling material such as magnetic earth or clay are mixed. The resin emulsion has a function as a binder for modeling material.

  As the acrylic resin, an acrylic resin emulsion or an acrylic copolymer resin emulsion can be used. As the urethane resin, a urethane resin emulsion or a urethane copolymer resin emulsion can be used. As the silicone resin, a silicone resin emulsion or a silicone copolymer resin emulsion can be used.

  In the resin emulsion, at least one of the acrylic resin or the urethane resin may be mixed, but the silicon resin is an essential component that must be mixed.

  Acrylic resin exhibits a function as a binder for modeling materials, etc., but contributes to the addition of hardness etc. to a modeled object manufactured using a mud composition. It is possible to ensure the breaking strength. The mixing of urethane resin demonstrates the function as a binder for modeling materials, etc., but it also contributes to imparting elasticity, softness, etc. to molded objects manufactured using a mud composition. In addition, the bending strength can be ensured.

  When the acrylic resin is not mixed, the modeled object may be too soft. However, depending on the use of the modeled object, a configuration in which the acrylic resin is not mixed may be considered. When the urethane-based resin is not mixed, the molded product may be too hard. However, depending on the use of the molded product, a configuration in which the urethane-based resin is not mixed may be considered. In order to impart moderate hardness, it is preferable to use emulsions of both acrylic resins and urethane resins.

  Silicone resin not only functions as a binder for modeling materials, but can also give elasticity, softness, etc. to molded objects manufactured using a mud composition, like urethane resins. In addition, it is possible to secure bending strength. On the other hand, such a silicon-based resin greatly contributes to imparting releasability from a gypsum mold that has not been sufficiently obtained with the above acrylic resin and urethane resin.

  Furthermore, it also functions as an antifoaming material. Since the mud composition has a composition formed by mixing a resin emulsion with a modeling material using a resin emulsion as a binder, the viscosity is inevitably higher than that of water, for example, air is easily involved in stirring during mixing, and bubbles are easily generated. Generated bubbles are hard to disappear.

  In addition, such foam is generated when the slurry composition is circulated by pouring the slurry composition into the mold and rotating the mold so that the slurry composition is lightly shaken so as to adhere to the inner surface of the mold. It is likely to occur due to the wettability with the mold inner surface. If the foam is cured in a state in which such bubbles are generated, fine crushing based on the foam remains on the surface of the molded article after demolding, and it becomes difficult to form a model with a smooth skin. For example, it becomes a fatal defect in the construction of a doll face or the like that particularly requires smoothness of the background. In the slurry composition according to the present invention, the function as an antifoaming agent is exerted on the silicon-based resin used as the binder.

  In the mud composition of the present invention, the silicone resin is adopted as an essential component in the hope of exerting its function as an antifoaming agent, but from the viewpoint of releasability, Although there is a means for applying a silicon-based resin on the surface, it is preferable that such an application means is not mixed with the surface condition of the shaped article after demolding and is mixed in the slurry composition.

  As described above, the molding material mixed with the mixed emulsion composed of the resin described above is composed of magnetic earth or clay, and the mud composition is adhered to the inner surface of the mold with a predetermined layer thickness. If it is dried in a state, it becomes a molded article having an outer surface that hardens and finely reproduces the irregularities on the inner surface of the mold.

  The material for modeling may be any material that adheres to the inner surface of the mold in a mud state and is then cured by drying, and examples thereof include magnetic earth and clay. The magnetic earth is a material used for producing porcelain that is a ceramic, and for example, a powder obtained by pulverizing stones having a large amount of feldspar is well known. Clay is a material used in the production of pottery that is pottery. Various clays with slightly different compositions are produced in various parts of Japan, and such clay may be used. For example, Shino clay used for pottery well known as Shino ware can be exemplified as clay.

  As described above, the material for modeling includes magnetic earth or clay, but may also include rock powder. For example, in the pottery, a configuration in which rock powder is appropriately included in addition to magnetic earth or clay is employed, but the rock powder employed in such a configuration may be used.

  When mixing the modeling material having such a configuration with the resin emulsion described above, the modeling material is mixed with the resin emulsion in a state where the modeling material is once uniformly dispersed in water using an anionic surfactant.

  Furthermore, the present inventors have found that the addition of artificial mineral fibers such as potassium titanate fibers is effective in adjusting the viscosity of the mud composition having the above-described configuration. When the viscosity of the mud composition is too small, it is difficult to adhere to the inner surface of the mold with a predetermined layer thickness. On the other hand, when the viscosity is too large, it is difficult to wrap around the slurry composition when it is poured into the mold so that the slurry composition adheres to the inner surface of the mold with a predetermined layer thickness.

  For this reason, the mud composition requires viscosity adjustment in some cases so that the viscosity falls within an appropriate range. In such viscosity adjustment, the present inventor has made an artificial product such as potassium titanate fiber. We found that mineral fibers are effective. When such an artificial mineral fiber is used, not only the viscosity adjustment but also the strength and surface hardness of a shaped article formed by molding can be improved. Furthermore, it is possible to reduce the volume shrinkage rate when it is dried after adhering to the inner surface of the mold, and the mold releasability can be further improved.

  Unlike the conventional configuration, it is one of the objects of the present invention to facilitate the demolding. However, in order to facilitate the demolding, the slurry composition attached to the inner surface of the mold is dried and cured. In the state, it is necessary to involve a certain amount of volume shrinkage within a range in which demolding is easy. At the time of drying and curing, if the volume of the slurry composition expands, it becomes difficult to detach from the inner surface of the mold, but demolding becomes easy by shrinking the volume within a certain range.

  In general, it is said that when the volumetric shrinkage is increased, the releasability is improved, but in the case of a mold having a complex uneven shape such as a complex mold such as a doll's face and limbs, The inventors considered that if the shrinkage rate is increased too much, the mud composition moves in the mold as much as it cures, and the slight unevenness of the mold surface acts as an undercut, making it difficult to remove the mold. The present inventor has found through experiments that, for example, when the volumetric shrinkage rate is suppressed to within about 8%, the releasability in a complicated mold such as a doll mold can be improved.

  It has been found that the addition of artificial mineral fibers such as potassium titanate as described above is effective in adjusting the volumetric shrinkage rate as well as adjusting the viscosity of the mud composition, ensuring the strength after molding, and ensuring the surface hardness. .

  By using the slurry composition of the above configuration, the slurry composition adheres to the inner surface of the gypsum mold with good releasability, and is dried and cured, resulting in a fine copy of the irregularities on the inner surface of the mold. Can be formed as a shaped article. Furthermore, in order to express a special texture on the surface of the shaped object, for example, an arbitrary amount of plant fibers such as pulp fibers may be added. The addition of plant fibers such as pulp fibers leads to an improvement in strength of the modeled object itself as well as a textured effect on the modeled object surface. In addition, the present inventor confirmed that it functions effectively to reduce the volumetric shrinkage during dry curing. That is, it was effective for improving the releasability.

  The slurry composition according to the present invention can be produced as follows. That is, the modeling material such as magnetic earth or clay described above is immersed in an aqueous solution in which an emulsion of a silicon-based resin is dissolved in water so as to be easily dispersed. If necessary, an anionic surfactant may be added to the aqueous solution of the silicone resin emulsion.

  In this way, the water-containing modeling material in which the required moisture is contained in the modeling material is stirred for a predetermined time with a mixing stirrer under the conditions of vacuum and room temperature. After confirming that the material for modeling has been uniformly dispersed by such stirring, inorganic powder to be mixed with rock powder, plant fiber powder such as pulp powder, artificial mineral fiber such as potassium titanate, and further as required In response, the required amount of preservative and fungicide is added and stirred. The stirring time may be performed until uniform dispersion can be confirmed.

  In the state in which the stirring components are uniformly dispersed by the stirring, at least one of an acrylic resin emulsion and a urethane resin emulsion, a peptizer, and water are further added and stirred. In a state where it is confirmed that the mixed components are uniformly dispersed and no bubbles are generated, unnecessary substances mixed by passing through a sieve of a predetermined mesh are removed, and the filtrate is used as a mud composition.

  The mud composition having such a configuration is used in a modeling method for producing a molded product in accordance with a mold by using it as follows. For example, as the mold, a gypsum mold that imitates the face of a doll on the inner surface of the mold is prepared. Such a plaster mold may be formed into a split mold that can be divided into a plurality of parts when demolding.

  The slurry composition having the above structure is poured into such a mold. Lightly rotate the mold, etc. so that the slurry composition in the mold spreads over the inner surface of the mold, adheres the slurry composition to the inner surface of the mold, and removes the excess slurry composition in the mold. Take out. By repeating the adhesion of the slurry composition to the inner surface of the mold a predetermined number of times, the slurry composition is adhered to the inner surface of the mold in a predetermined layer thickness.

  After depositing the slurry composition to a predetermined layer thickness on the inner surface of the mold, the slurry composition is dried by natural drying or forced drying. The mud composition hardens upon drying. When cured, the mold is broken and removed. By removing the mold, the unevenness of the mold is precisely reproduced on the surface, and a hollow molded product having a hollow inside is obtained as a molded article.

  The molded article as such a hollow molded article is different from a ceramic or the like, and is subjected to coloring, painting, etc. with an appropriate pigment, dye, paint, etc. in a demolded state without firing in a kiln, etc. If a wig or the like is attached accordingly, the face of the doll can be easily produced. In this description, the case where a mold that imitates the face of a doll is used has been described as an example. However, what is used as a mold may of course be an arbitrary shape.

  As described above, the mud composition of the present invention has a component configuration with special consideration for adjusting the volume shrinkage during drying and curing and improving the releasability. Even in the case of a complicated shape, that is, in the case of a mold having fine irregularities in which an undercut portion or the like is easily formed and is difficult to be removed, it can be sufficiently applied.

  With regard to breakage at the time of demolding, it is possible to improve the bending strength of molded products by adopting silicon-based resin that functions as a binder, defoaming material, etc. as an essential component of the mixed emulsion. In order to prevent damage during removal and mold removal.

  Next, the slurry composition based on the structure demonstrated by the said embodiment was prepared, and as shown in the following Examples about each, the effect of mold release property etc. was verified.

  In the mud composition of this example, as shown in Example 1 of FIG. 1, a silicone copolymer resin emulsion, a styrene / acryl copolymer resin emulsion, and a urethane copolymer resin emulsion are used as the resin emulsion. Yes. White porcelain earth is used as a material for modeling.

  In the mud composition according to Example 1 using such a constituent material, first, a white porcelain clay is added with a predetermined amount of water to produce a hydrous white porcelain clay. The entire amount of white porcelain clay is immersed in an aqueous solution in which the total amount of the silicone copolymer resin emulsion used is dissolved in water. The water-containing white porcelain earth formed by soaking is stirred with a mixing stirrer for a predetermined time. White porcelain earth is blended at a ratio of 53.4 parts by weight, water at 14.83 parts by weight, and an emulsion resin of silicon copolymer resin at 0.30 parts by weight.

  As the resin emulsion of the silicone copolymer resin, for example, an emulsion of silica-containing dimethylpolysiloxane was used. A resin emulsion having a composition of 1% or less of silica, 10 to 20% of polyoxyalkylene dimethylpolysiloxane, and 60 to 70% of water was used.

  In the present example, the addition amount of the silicon-based copolymer resin was suppressed to such an extent that the release property and antifoaming function of the silicon-based resin could be exhibited. When the resin solid content of the silicone resin emulsion is 20 to 40 parts by weight, the silicone resin emulsion constituting the mud composition is 0.05 parts by weight relative to the total amount of the other resin emulsions. -10 parts by weight is a usable range. More preferably, it is 0.05 to 5 parts by weight. This is a consideration from the viewpoint of manufacturing cost, but it is possible to increase the amount of addition, and by increasing the amount of addition, the bending strength of the molded product can be increased as with the addition of urethane resin. Further improvement can be achieved.

In the case of Example 1, using an emulsifier manufactured by Shinko Machinery Co., Ltd., stirring was performed for 30 minutes under conditions of a vacuum degree of 8.0 × 10 ^{4 to} 8.7 × 10 ⁴ Pa (600 to 650 mmHg) and room temperature. did. With white porcelain clay uniformly dispersed, 7.12 parts by weight kaolin, 1.19 parts by weight powdered pulp, 0.59 parts by weight potassium titanate fiber, 0.35 parts by weight preservative, 0.18 A part by weight of the fungicide was put into the mixing stirrer and stirred for 30 minutes under the same conditions as described above. When the dispersion is not uniform, the stirring time may be appropriately extended until uniform dispersion is ensured.

  As powder pulp, No. 80 pulp fiber powder was used. The pulp fiber powder used is natural cellulose fiber powder, but synthetic fiber powder such as vinylon may be used in combination as long as it does not hinder the surface condition of the molded product. Addition of such powdered pulp is added to produce a texture on the surface of the molded product, but it also gives the molded product breaking strength and bending strength, and can also reduce the volumetric shrinkage of the molded product. .

  For example, Tismo N (registered trademark) manufactured by Otsuka Chemical Co., Ltd. was used as the potassium titanate fiber. As the artificial mineral fiber, titanium fiber, natural mineral fiber, etc. may be used. Addition of such artificial mineral fibers such as potassium titanate is effective for improving the fracture strength, bending strength, and surface hardness of molded products as described above, but also has the effect of increasing the viscosity of the mud composition. Demonstrated.

  In terms of strength improvement, it is effective to use potassium titanate fibers subjected to silane coupling treatment. Further, in the mud composition according to the present invention, a silicon-based resin is employed as an essential component, and the resin emulsion of such a silicon-based resin also plays a role of silane coupling.

  In this example, as a preservative, for example, a 10% aqueous solution of chloro, methyl, iso, and thiazoline that is a sulfur-based mixture was used. As the fungicide, for example, a powder in which 30% thiabenzazole and 70% talc were uniformly blended was used. However, the preservative and the fungicide are not essential components, and either one or both may be omitted as appropriate.

  In this state, 11.86 parts by weight of a resin emulsion of a styrene / acrylic copolymer resin and 1.19 parts by weight of a resin emulsion of a urethane copolymer resin with the above additives uniformly dispersed. And 0.09 parts by weight of a peptizer and 8.9 parts by weight of water are further added and stirred for 60 minutes under the same conditions as described above. After stirring as described above, a slurry composition of Example 1 was obtained by passing through a 48-mesh sieve while confirming that no bubbles were generated.

  As a resin emulsion of a styrene / acrylic copolymer resin, for example, Polysol AP-4710 (solid content 50%, pH 9, average particle size 0.1 to 0.2 μm) manufactured by Showa Polymer Co., Ltd. was used. As the resin emulsion of urethane copolymer resin, for example, Adekapon titer HUX-240 (solid content 30%, pH 7-8, average particle size 0.1 μm) manufactured by Asahi Denka Kogyo Co., Ltd. was used.

The acrylic resin resin emulsion and the urethane resin resin emulsion may be those having an average solid content of these mixtures of about 30 to 50%. The blending ratio varies depending on the strength of the molded product, the complexity of the unevenness of the molded product related to the ease of demolding, etc., but 3 to 25 parts by weight is considered preferable.
As a peptizer, for example, sodium silicate was used.

  In the mud composition of this example, as shown in Example 2 of FIG. 1, as in Example 1, a silicone copolymer resin emulsion and a styrene / acryl copolymer resin emulsion (AP-4710) were used as the resin emulsion. Urethane-based copolymer resin emulsions are used. White porcelain earth is used as a material for modeling.

  In the mud composition according to Example 2 using such a constituent material, first, a white porcelain clay is added with a predetermined amount of water to produce a hydrous white porcelain clay. The whole amount of the white porcelain clay is immersed in an aqueous solution in which the total amount of the anionic surfactant and the resin emulsion of the total amount of the silicon resin to be used are dissolved. The water-containing white porcelain earth formed by soaking is stirred with a mixing stirrer for a predetermined time. White porcelain earth is blended in a proportion of 53.4 parts by weight, water is 14.83 parts by weight, an anionic surfactant is 0.1 part by weight, and a silicone resin emulsion resin is blended in a ratio of 0.30 part by weight.

  As the anionic surfactant, for example, a 30% aqueous solution of sodium lauryl sulfate was used. Other anionic surfactants may be employed as long as they can improve the familiarity of the inorganic substance mixed in the mud composition with water and can ensure the effect of easy removal of the entrained air during stirring. Absent. The blending ratio is preferably 0.1 to 0.3 parts by weight with respect to the inorganic powder constituting the mud composition.

  As the resin emulsion of the silicone copolymer resin, for example, an emulsion of silica-containing dimethylpolysiloxane was used. A resin emulsion having a composition of 1% or less of silica, 10 to 20% of polyoxyalkylene dimethylpolysiloxane, and 60 to 70% of water was used.

As in the case of Example 1, using an emulsifier manufactured by Shinko Machinery Co., Ltd., for 30 minutes under conditions of a vacuum degree of 8.0 × 10 ^{4 to} 8.7 × 10 ⁴ Pa (600 to 650 mmHg) and room temperature. To the stirred hydrous white porcelain, 7.12 parts by weight kaolin, 1.19 parts by weight powdered pulp, 0.59 parts by weight potassium titanate fiber, 0.35 parts by weight preservative, 0.18 parts by weight The antifungal agent was put into the mixing stirrer and stirred for 30 minutes under the same conditions as described above. The same powdery pulp, potassium titanate fiber, preservative and antifungal agent as in Example 1 were used.

  In the same manner as in Example 1 with stirring and the above-mentioned additive uniformly dispersed, 11.86 parts by weight of a styrene / acrylic copolymer resin emulsion and 1.19 parts by weight Add urethane resin emulsion, 0.09 parts by weight of peptizer, and 8.9 parts by weight of water, and stir for 60 minutes under the same conditions as above. In the state confirmed, the slurry composition of Example 2 was manufactured by passing through a 48-mesh sieve.

  The slurry composition of this example was produced in the same manner as in Example 2 as shown in Example 3 of FIG. In the case of Example 2, potassium titanate is added, but in the case of Example 3, the difference is that potassium titanate is not added.

  In the present example, unlike the first to third examples, a square clay was used as a modeling material. In addition, quartzite powder was also used. The mud composition having such a structure was first made into hydrous clay by adding a predetermined amount of water to the clay. The entire amount of cocoon clay and quartzite powder is immersed in an aqueous solution in which the total amount of the silicone copolymer resin emulsion used is dissolved in water. The hydrous clay formed by soaking is stirred with a mixing stirrer for a predetermined time. Sasame clay is blended at a ratio of 13.7 parts by weight, silica powder at 22.8 parts by weight, water at 24.3 parts by weight, and a silicone copolymer resin emulsion resin at 0.30 parts by weight.

  As the resin emulsion of the silicon copolymer resin, for example, an emulsion of silica-containing dimethylpolysiloxane was used in the same manner as in Example 1. A resin emulsion having a composition of 1% or less of silica, 10 to 20% of polyoxyalkylene dimethylpolysiloxane, and 60 to 70% of water was used.

  In a state where the hydrous clay was uniformly dispersed, 18.4 parts by weight of kaolin was added and further stirred. In addition, 13.9 parts by weight of a styrene / acrylic copolymer resin emulsion, 6.5 parts by weight of a urethane resin resin emulsion, and 0.4 parts by weight of peptization were further added to the agitated product. The slurry composition of Example 4 was produced by further adding the agent, stirring for 60 minutes under the same conditions as described above, and passing through a 48-mesh sieve.

  In this example, for example, Polysol AP-3750 (solid content 50%, pH 8-10, average particle size 0.14 μm) manufactured by Showa Polymer Co., Ltd. was used as the resin emulsion of styrene / acrylic copolymer resin. . As the resin emulsion of urethane copolymer resin, the same one as in Example 1 was used.

  In order to compare with the slurry compositions of Examples 1 to 4 according to the present invention having the above-described configuration, a slurry composition having a conventional configuration was produced as Comparative Examples 1 to 3.

(Comparative Example 1)
In the slurry composition of Comparative Example 1, as shown in Comparative Example 1 of FIG. 1, a styrene / acrylic copolymer resin emulsion and a urethane copolymer resin emulsion are used. Silicone resin emulsion is not used. White porcelain earth is used as a material for modeling.

  In the mud composition related to Comparative Example 1 using such constituent materials, first, a white porcelain clay is added with a predetermined amount of water to produce a hydrous white porcelain clay. The hydrous white porcelain clay formed by immersing the entire amount of white porcelain clay in water is stirred for a predetermined time with a mixing stirrer. White porcelain earth is blended in a proportion of 51.4 parts by weight and water is 12.3 parts by weight.

As in the case of Example 1, using an emulsifier manufactured by Shinko Machinery Co., Ltd., for 30 minutes under conditions of a vacuum degree of 8.0 × 10 ^{4 to} 8.7 × 10 ⁴ Pa (600 to 650 mmHg) and room temperature. 9.1 parts by weight of kaolin, 1.2 parts by weight of titanium oxide, 0.4 parts by weight of a preservative, and 0.2 parts by weight of a fungicide are added to the stirred water-containing white porcelain clay into the above mixed stirrer. The mixture was stirred for 30 minutes under the same conditions as above. In this comparative example 1, powder pulp and potassium titanate fiber are not mixed.

  With stirring in this manner, with the above additives uniformly dispersed, 8.2 parts by weight of a styrene / acrylic copolymer resin emulsion and 0.3 parts by weight of a urethane resin emulsion , 0.1 parts by weight of peptizer, 15.4 parts by weight of water, and 1.5 parts by weight of water for adjustment were further added and stirred for 60 minutes under the same conditions as above, In a state where it was confirmed that there was no generation of bubbles, a slurry composition of Comparative Example 1 was produced by passing through a 48-mesh sieve.

  The resin emulsion of styrene / acrylic copolymer resin and the resin emulsion of urethane resin used were the same as those used in Example 1.

(Comparative Example 2)
In Comparative Example 2, 56.0 parts by weight of white porcelain earth as a modeling material was immersed in 20.0 parts by weight of water to form hydrous white porcelain earth. The hydrous white clay was stirred with the same mixing stirrer as in the above example, and 10.0 parts by weight of kaolin and 1.3 parts by weight of titanium oxide were added and further stirred in a uniformly dispersed state.

  In addition to the agitated product, a 12.2 parts by weight styrene / acrylic copolymer resin emulsion (AP-4710) and a 0.3 part by weight urethane resin resin emulsion similar to those of the above-described example were added. Then, 0.2 parts by weight of the peptizer was further added, and the mixture was stirred for 60 minutes under the same conditions as described above, and passed through a 48-mesh sieve to produce a slurry composition of Comparative Example 2.

(Comparative Example 3)
In Comparative Example 3, 13.7 parts by weight of the clay was used as a material for modeling, and 22.8 parts by weight of silica powder was immersed in 24.3 parts by weight of water to form a hydrous clay. . The hydrous clay was stirred with the same mixing stirrer as in the above example, and in a uniformly dispersed state, 18.4 parts by weight of kaolin was added and further stirred. In addition, 13.9 parts by weight of a styrene / acrylic copolymer resin emulsion (AP-3750), 6.5 parts by weight of a urethane resin emulsion, and 0.4 wt. A part of the peptizer was further added, stirred for 60 minutes under the same conditions as above, and passed through a 48-mesh sieve to produce a slurry composition of Comparative Example 3.

  The resin emulsion of styrene / acrylic copolymer resin and the resin emulsion of urethane resin were the same as in Example 4.

  The main physical properties of each of the mud compositions produced in Examples 1 to 4 and Comparative Examples 1 to 3 are shown in FIG.

  Among the physical properties shown in FIG. 2, the specific gravity was determined by putting the slurry composition into a 50 ml graduated cylinder and measuring its volume and its weight to determine the specific gravity as weight / volume. The fluidity is determined by visually observing the inflow state when the slurry composition flows into the mold, so that each composition of the slurry composition is uniformly dispersed, there is no partial dispersion failure, and the fluidity is uniform. Those showing uniform fluidity in viscosity were evaluated as good (◯). The stability over time was determined to be good (◯) when the slurry composition was left in a graduated cylinder for 1 week and no layer separation occurred.

  The volume shrinkage was calculated by (3a / X) × 100, where X is the length of one side of the modeled object and a is the amount of change in the length due to shrinkage. Fracture strength and bending strength were measured using a SUN RHEO METER COMPAC-100 MODEL CR-100 (SUN SCIENTIFIC CO, LTD.) After processing the shaped object to 60 mm × 25 mm × 3 mm. The warp / distortion is 1 mm when the test piece is processed to 60 mm x 25 mm x 3 mm on the surface plate and one end in the longitudinal direction is pressed on the surface plate, and the gap generated between the bottom of the other end and the surface plate is 1 mm. The following were considered good (◯).

  Among the physical properties shown in FIG. 2, the surface hardness of the test piece surface of 60 mm × 25 mm was evaluated as good (◯) when the core hardness was not easily damaged by a pencil standardized with H. As for the abrasion resistance, the surface of a test piece of 60 mm × 25 mm was rubbed once with # 100 sandpaper, and the one that was not easily damaged was evaluated as good (◯).

  The releasability is a gypsum mold imitating a commercially available doll head, and the releasability was evaluated in the situation when the gypsum mold was opened at the time of demolding. In particular, the evaluation is indicated by ○ when the situation where the mold can be taken out without applying force is shown. If it shows a situation where it cannot be removed from the mold unless a considerable force is applied, or if damage such as chipping, cracking, etc. of the molded product due to the difficulty of partial release is slight, the evaluation is △ Indicated. In the case where the state where the molded product cannot be taken out from the mold or the state where the mold is damaged is shown, the evaluation is indicated by x.

  Compared with the slurry compositions of Comparative Examples 1 to 3, the volume shrinkage ratio that greatly affects the mold release properties of the slurry compositions described in Examples 1 to 4 is 14, 15 of Comparative Examples 1 to 3. On the other hand, it is as small as 8, 10, and 13. In the inventor's experiment, sufficient mold releasability is obtained as long as it has a volumetric shrinkage ratio of 8 or more and 13 or less even for a mold having complicated irregularities so that an undercut portion is likely to occur. It was confirmed to show.

  In particular, in Examples 1 to 3 and Comparative Examples 1 and 2, white porcelain earth is used as a material for modeling, but the bending strength is improved by about 2 times and includes releasability. The overall evaluation is improved to ○. Such an improvement in bending strength is presumed to be due to the addition of a silicon-based resin as an essential component to the mud composition. Both the water supply times of the modeling materials were 20 minutes, and the time required for demolding when the mud composition was dried and cured was 1 hour.

  Regarding the actual releasability, Examples 1 to 3 were good (◯). However, although Comparative Example 1 shows good release properties in some cases, the release properties are slightly inferior in some cases (Δ), or the release properties are completely inferior (×). The releasability was not stable. Comparative Example 2 also had poor release properties.

  In addition, it can also be seen that both the breaking strength and the bending strength are increased in the case of Examples 1 and 2 when the potassium titanate fiber is added, compared to Example 3 where the potassium titanate is not added. .

  As can be seen from the examination of the Example and Comparative Example shown in FIG. 2, the release property is improved in the case of the configuration according to the present invention using the resin emulsion of the silicone resin in the mud composition. I understand. Furthermore, it was confirmed that the fracture strength and bending strength can be improved when potassium titanate fiber is added.

Example 4 and Comparative Example 3 both show the case where the clay is used as a modeling material, but Example 3 to which the silicone copolymer resin emulsion is added is a comparative example in which such addition is not performed. Compared to 3, it was confirmed that the volumetric shrinkage rate was kept low and the releasability was improved.
In Example 4, as in Comparative Example 3, a sufficiently high bending strength was obtained, but potassium titanate was further added to improve the viscosity and further reduce the volume shrinkage rate. Of course, it may be configured so as to be applicable to a mold having unevenness.

  As mentioned above, the invention made by the present inventor has been specifically described based on the embodiment. However, the present invention is not limited to the embodiment, and various modifications can be made without departing from the scope of the invention. Needless to say.

  INDUSTRIAL APPLICABILITY The present invention can be effectively used as a modeling method that can form a molded article without firing by curing the slurry composition in a state where it is adhered to the mold inner surface or the like.

It is explanatory drawing which shows the mixing | blending comparison of the mud composition of the Example concerning this invention, and the mud composition of the conventional structure. It is explanatory drawing which shows comparative evaluation, such as a physical property of the mud composition of the Example concerning this invention, and the mud composition of a conventional structure, and mold release property.

Claims (6)

A mud composition used in a molding method for modeling by adhering to a surface such as the inner surface of the mold or the outer surface of the object and curing it,
A resin emulsion of at least one of acrylic resin and urethane resin;
A resin emulsion of silicone resin;
Slip composition characterized in that the shaping material consisting disilazide or clay are mixed.
In the mud composition according to claim 1,
A mud composition containing potassium titanate. In the mud composition according to claim 1 or 2,
A mud composition comprising plant fibers such as pulp fibers. In the mud composition according to any one of claims 1 to 3,
Mixing of the resin emulsion and the modeling material is carried out in a state where the modeling material is dispersed in water with an anionic surfactant.   The slurry composition according to any one of claims 1 to 4 is poured into a mold, cured in a state where the slurry composition is attached to the inner surface of the mold, and molded after being cured and demolded. A characteristic modeling method.   The mud composition according to any one of claims 1 to 4 is cured and shaped in a state of being adhered to an outer surface of a shaped article formed of a flexible material such as paper or cloth, and Modeling method to do.

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