Login| Sign Up| Help| Contact|

Patent Searching and Data


Title:
A COMPOSITE STONE WITH THICK, LONG, AND IRREGULAR VENOUS STRUCTURE RESEMBLING CALACATTA MARBLE AND THE PRODUCTION METHOD OF THIS COMPOSITE STONE
Document Type and Number:
WIPO Patent Application WO/2021/076070
Kind Code:
A1
Abstract:
The invention is a method of producing a composite with a thick, long, and irregular appearance with a venous structure as on the surface of Calacatta marble. The purpose of the present invention is to produce a composite stone with thick, long, and irregular appearance similar to that of Calacatta marble by opening the physical channels and filling the channels with the vein formula according to the rheological properties of the base formula.

More Like This:
Inventors:
ARICI, Esra (IV. Kisim Kecilikoy OSB Mah. Ahmet Nazif Zorlu Bulvari No:22, Yunusemre/Manisa, TR)
OLMEZ, Duygu (IV. Kisim Kecilikoy OSB Mah. Ahmet Nazif Zorlu Bulvari No:22, Yunusemre/Manisa, TR)
DENIZ, Gokhan (IV. Kisim Kecilikoy OSB Mah. Ahmet Nazif Zorlu Bulvari No:22, Yunusemre/Manisa, TR)
ALTINYAY, Arman (IV. Kisim Kecilikoy OSB Mah. Ahmet Nazif Zorlu Bulvari No:22, Yunusemre/Manisa, TR)
TOPCU, Nurcan (IV. Kisim Kecilikoy OSB Mah. Ahmet Nazif Zorlu Bulvari No:22, Yunusemre/Manisa, TR)
Application Number:
TR2019/050967
Publication Date:
April 22, 2021
Filing Date:
November 18, 2019
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
PEKER YUZEY TASARIMLARI SANAYI VE TICARET ANONIM SIRKETI (IV. Kisim Kecilikoy OSB Mah. Ahmet Nazif Zorlu Bulvari No:22, Yunusemre/Manisa, TR)
International Classes:
B28B1/00
Attorney, Agent or Firm:
ANKARA PATENT BUREAU (Kavaklidere, Ankara, TR)
Download PDF:
Claims:
CLAIMS

1. A method of producing a composite having a venous structure with a thick, long, and irregular appearance as on the surface of Calacatta marble, characterized in that it comprises the following steps;

- Preparation of a vein containing, respectively by weight;

• at least one mineral 45 pm in size selected from the group consisting of quartz, silica sand, quartzite, quartz sand, amorphous quartz, b-Quartz, a-cristobalite, b-cristobalite, a-tridymite, b-tridymite, milky quartz, transparent quartz and various combinations of them at the rate of 20-40%,

• at least one mineral 100-400 pm in size selected from the group consisting of quartz, silica sand, quartzite, quartz sand, amorphous quartz, b-Quartz, a-cristobalite, b-cristobalite, a- tridymite, b-tridymite, milky quartz, transparent quartz and various combinations of them at the rate of 60-80%, and

• 6-26% resin;

- Preparation of a vein containing, respectively by weight;

• at least one mineral 45 pm in size selected from the group consisting of quartz, silica sand, quartzite, quartz sand, amorphous quartz, b-Quartz, a-cristobalite, b-cristobalite, a-tridymite, b-tridymite, milky quartz, transparent quartz and various combinations of them at the rate of 20-40%,

• at least one mineral 100- 400 pm in size selected from the group consisting of quartz, silica sand, quartzite, quartz sand, amorphous quartz, b-Quartz, a-cristobalite, b-cristobalite, a-tridymite, b-tridymite, milky quartz, transparent quartz and various combinations of them at the rate of 60-80%, and

• 6-16% resin,

- Spreading the base into the mould, - Following spreading, compressing the by applying pressure on the surface with the help of the roller,

- Opening different types of vein paths with the help of a robotic arm,

- Filling the vein prepared in accordance with the base into the opened veins,

- Then, applying the vibratory pressing process under vacuum to obtain vein appearance,

- Curing process at low temperatures to finalize the quartz surface,

- Calibration and polishing,

- Obtaining the final product; a composite stone having a vein structure with thick, long and irregular appearance.

2. Method of producing a composite having a venous structure with a thick, long, and irregular appearance according to Claim 1, characterized by the use of at least one pigment selected from a group consisting of iron oxide, titanium dioxide, copper chromium oxide, carbon black, manganese iron oxide (in spinel and hematite structure), chromium iron oxide (in hematite structure) pigments in the vein and base formulations in order to obtain the vein colours of Calacatta marble on the composite stone surface.

3. Method of producing a composite having a vein structure with a thick, long, and irregular appearance according to Claim 1, characterized by reducing the resin viscosity to 50-150 Cp by adding a styrene monomer at the rate of 5-40% by weight into the unsaturated polyester resin which has a viscosity in the range of 500-700 Cp and is used in vein .

Description:
A COMPOSITE STONE WITH THICK, LONG, AND IRREGULAR VENOUS STRUCTURE RESEMBLING CALACATTA MARBLE AND THE PRODUCTION METHOD OF THIS COMPOSITE STONE

Field of The Invention

The invention relates to a composite stone having an irregular and long-veined appearance similar to that of the Calacatta marble surface and cross-section, and its production method.

Background of the Invention

Composite stone slabs are formed by mixing quartz raw materials of various sizes, binders, and additives. Engineered Stone Slabs are a type of composite stone, usually containing quartz, binder (resin) and additives (catalyst, accelerator, etc.) in various sizes. Engineered Stone Slabs are used as substitutes for natural stone slabs. However, in terms of physical and chemical properties, they are far superior to natural stones.

The production steps of quartz stone are the mixing of quartz and binders of various sizes, transferring the prepared mixture into the mould, removing the air in the mixture by vibratory compaction process under vacuum, heat curing process, and polishing process. Granular quartz particles of 65% by weight and small size quartz powder of 25% by weight are used in "Quartz Stones". In addition, resin about 9% by weight and additives about 1% by weight are added. The key point of the Quartz Stone production method is the vibratory compaction step performed under vacuum. During the vibratory compaction, the density of quartz particles is increased while the absorption of the air that is wanted to be removed because it is vacuumed is provided. In quartz stones with high packing density, an improvement is observed especially in mechanical and aesthetic properties because the rate of gaps will be minimal. When the techniques of composite stone production are examined, it is seen that many patents and studies have already been realized. In the scope of the above- described patent application, the patent application ES2187313 discloses the production of composite stone (or artificial stone) made by using quartz and polyester resin of different sizes. Vein applications developed to provide natural stone appearance on composite stone have received a lot of attention recently.

In one of the applications of vein forming techniques, first, the base parts of the composite stone were filled by placing templates in the mould, and then the venous parts. After the vein was added, the templates were removed, and vibratory compaction was performed. Finally, the curing process was performed, and the stone reached its final form. However, shifts in the patterns occurred during the vibratory compaction process after the templates used in this technique were removed from the mould. In another template application, it is mentioned that the appearance and dimensions of the vein were determined in the mould using a template and then filled with the mixture formed by using quartz, resin, and additives. Correction apparatuses were used to remove the appearance of the templates after the vein application.

Many different techniques have also been invented besides template applications. For example, in the patent application US9186819B1, a mixture of powder, resin, and additives was placed in a closed mould in the upright position to form layers. After this process, the three-dimensional vein image was obtained when the mould was brought to the horizontal position. Considering that the weight and aesthetic appearance of the composite stone depend on the surface structure, this study poses some difficulties in turning the mould and removing the gaps in the composite stone. In patent application EP2944443A1, a thin and thick three- dimensional vein image was obtained with the help of a conveyor belt.

Another method used during vein formation is the use of apparatus for forming channels. In the patent application US10099236B1, channels were formed on the artificial stone surface by means of two cylindrical bar apparatus placed under the composite stone slab and these channels were filled with material by means of sprayers containing more than one hole. A three-dimensional vein structure was formed on the final product.

In recent years, with the development of quartz surface products, it has been observed that new and innovative appearances are preferred by the users rather than the classic granite appearance and design in the composite stone industry. As a result, very long veins with irregular appearance have become fashionable again. As a result of the depletion of Calacatta marble reserves in the Veneto region of northern Italy, the need for the artificial production of similar products has emerged. These types of products are made with different materials, including ceramic and acrylic. These materials have disadvantages compared to quartz stones in terms of strength. For this purpose, real designs have become a necessity in the most innovative products. Due to the increasing demand for products similar to Calacatta marble in the market, especially by users in the USA, various R & D studies are being carried out for the production of composite stones with aesthetic properties similar to that type of marble which is running out of reserves.

Thus, because of the depletion of Calacatta marble reserves, it became possible to produce artificial composite stones with the same pattern instead. In addition, the patterns and characteristics of the marbles extracted from the ore may vary, while all of the composite stones have the same pattern and characteristics.

With the invention of base and vein formulations, natural marble appearance has been provided for the first time on composite stone surfaces. Three-dimensional vein patterns on the surface of Calacatta marble were also provided in composite stone with the technique developed while the products produced with printing technology in ceramic coating or coated bench sector diverged from natural appearance. In addition, the venous texture similar to the surface of Calacatta marble can be obtained sustainably in every product. Summary of the Invention

The purpose of the invention is to develop a composite stone product with a vascular texture similar to that of the Calacatta marble surface.

Another purpose of the invention is to develop base formulations to provide vascular texture similar to that of Calacatta marble surface.

Another purpose of the invention is to develop vein formulations to provide vascular tissue similar to that of Calacatta marble surface.

Another purpose of the invention is to improve the rheological (viscosity) properties of the base and vein formulations.

Another purpose of the invention is to open the physical channels in the composite stone product according to the rheological properties of the base formula and to fill the channels with the vein formula.

Another purpose of the invention is to provide the channel shape and channel thickness necessary to form the vascular tissue similar to that of the Calacatta marble surface.

Detailed Description of the Invention

In order to achieve the purpose of the invention, "a Composite Stone with a Thick, Long and Irregular Vein Structure with the appearance of Calacatta Marble" is shown in the attached figures; and of these figures:

Figure 1 -Front and side views of composite stone with a thick, long and irregular vein structure like the Calacatta marble surface obtained within the scope of the invention. The invention is a method of producing a composite with a thick, long, and irregular venous structure as on the surface of Calacatta marble and includes the following steps:

- Preparation of a vein containing, respectively by weight;

• at least one mineral 45 pm in size selected from the group consisting of quartz, silica sand, quartzite, quartz sand, amorphous quartz, b- Quartz, a-cristobalite, b-cristobalite, a-tridimite, b-tridimite, milky quartz, transparent quartz and various combinations of 20-40% by weight,

• at least one mineral 100- 400 pm in size selected from the group consisting of quartz, silica sand, quartzite, quartz sand, amorphous quartz, b-Quartz, a-cristobalite, b-cristobalite, a-tridimite, b-tridimite, milky quartz, transparent quartz and various combinations of 60-80% by weight,

• %6-26 resin by weight;

- Preparation of a vein containing, respectively by weight;

• at least one mineral 45 pm in size selected from the group consisting of quartz, silica sand, quartzite, quartz sand, amorphous quartz, b- Quartz, a-cristobalite, b-cristobalite, a-tridimite, b-tridimite, milky quartz, transparent quartz and various combinations of 20-40% by weight,

• at least one mineral 100- 400 pm in size selected from the group consisting of quartz, silica sand, quartzite, quartz sand, amorphous quartz, b-Quartz, a-cristobalite, b-cristobalite, a-tridimite, b-tridimite, milky quartz, transparent quartz and various combinations of %60-80 by weight, and

• 6-16% resin by weight.

- Spreading the base into the mold,

- Then, compressing the by applying pressure on the surface with the help of the roller, Opening different types of vein paths with the help of a robotic arm,

Filling the vein prepared in accordance with the base into the opened veins,

Then, applying the vibratory pressing process under vacuum to obtain vascular appearance,

Curing process at low temperatures to finalize the quartz surface, Calibration and polishing,

And obtaining the final product as a composite stone with thick, long and irregular appearance with venous structure.

The invention is a method of producing composite with a thick, long, and irregular appearance with a venous structure as on the surface of Calacatta marble; Accordingly, within the scope of the invention, a base formulation was developed consisting of quartz and / or silica sand and / or quartzite and / or quartz sand and / or amorphous quartz and / or b-quartz and / or a-cristobalite and / or b-cristobalite and / or a-tridimite and / or b-tridimite and / or milky quartz and / or transparent quartz 45 pm in size and at the rate of %20-40 % by weight and 100- 400 pm in size and at the rate of %60-80 plus resin at the rate of 6-26% by weight. Furthermore, vein formulations were developed consisting of quartz and / or silica sand and / or quartzite and / or quartz sand and / or amorphous quartz and / or b-quartz and / or a-cristobalite and / or b-cristobalite and / or a-tridimite and / or b-tridimite and / or milky quartz and / or transparent quartz 45 pm in size at the rate of %20-40 % by weight and 100- 400 pm in size at the rate of %60-80 plus resin at the rate of 6-26% by weight. There was a difference between the base and the vein in resin changing between 0.1% and 10% by weight. The viscosity of the resin used in the vein was set to 400-600 cp depending on the vein formula, and the fluidity of the vein was optimized for the formation of long veins on the surface. In addition, a common matrix was formed between the vein and the base by wetting. Since using only quartz, a-quartz and / or silica sand and / or quartzite and / or quartz sand as raw materials in the base formula provided an opaque and unnatural appearance; amorphous quartz and / or b-quartz and / or a-cristobalite and / or b-cristobalite and / or a-tridimite and / or b-tridimite and / or milky quartz and / or transparent quartz were used and a natural appearance was obtained on the surface of the composite stone.

There was a difference of 0.1-10% by weight of resin between the vein and the base. The viscosity of the resin used was adjusted to 400-600 cp in the vein (a detail which is particularly important in the context of the invention) depending on the vein formula. When the difference in the amount of resin used in the vein and base was between 0.1% and 10% by weight and the viscosity of the resin was 400-600 cp, a common structure was formed between the vein and base by wetting. As the common structure composition of the vein and base was similar to that of the base, the expansion and cracking of the vein path that may occur after long-term use was prevented. Dryness and surface defects that may occur in the products during production were prevented.

The shape of the vein was arranged depending on the vein design (Figure- 1). Two different vein design were realized within the scope of the invention. The fine- textured vein map will be obtained with a roy-cut robot using powder pigments of different colors. The thick- textured vein map will be obtained with a roy-mix robot using different formulations. Thus, thanks to the vein and base formulations developed, products can have a natural marble appearance unlike standard quartz surfaces.

In order to solve the dryness and surface defects of the stones produced by using dry mixture formed in the laboratory, vein (wet mixture) formulations containing resin at the rate of 6-16% by weight with a viscosity of 400-600 Cp were formed according to the fluidity properties of the base formula containing quartz and / or silica sand and / or quartzite and / or quartz sand and / or amorphous quartz and / or b-quartz and / or a-cristobalite and / or b-cristobalite and / or a-tridimite and / or b-tridimite and / or milky quartz and / or transparent quartz 45 pm in size at the 20 - 40% and 100 - 400 pm in size at the rate of % 60-80 plus resin at the rate of % 6-26 by weight, respectively.

The resin content in the base was increased in the range of 0.1-10% in order to make the base better wetted. Thus, the resin content in the base was used as 6-26%. Since using only quartz, a-quartz and / or silica sand and / or quartzite and / or quartz sand as raw materials in the base formula provided an opaque and unnatural appearance; amorphous quartz and / or b-quartz and / or a-cristobalite and / or b-cristobalite and / or a-tridimite and / or b-tridimite and / or milky quartz and / or transparent quartz were used and a natural appearance was obtained on the surface of the composite stone.

Base and vein formulation studies were performed using quartz and / or silica sand and / or quartzite and / or quartz sand and / or amorphous quartz and / or b- Quartz and / or a-cristobalite and / or b-cristobalite and and / or a-tridimide and / or b-tridimide and / or milky quartz and / or transparent quartz in order to form a vein texture on the composite stone surface similar to the surface of Calacatta marble.

Iron oxide, titanium dioxide, copper chromium oxide, carbon black, manganese iron oxide (in spinel and hematite structure), chromium iron oxide (in hematite structure) pigments were used in vein and base formulations in order to obtain the vein colors of Calacatta marble on the composite stone surface.

The unsaturated polyester resin used as a standard in production has a viscosity in the range of 500-700 Cp. A lower viscosity resin was required to apply the resin with the robot. Therefore, the viscosity of the resin was reduced to 50-150 Cp by adding styrene monomer at the rate of 5 to 40% by weight into unsaturated polyester resin. Experimental Studies

Calacatta marble samples and corresponding raw material and colour pigments were examined in order to provide a vein texture similar to the surface of Calacatta marble and to form thick veins on the stone. In the laboratory, prototype base and vein formulations (dry mixture) were created. Vein maps were drawn by using the Rhinoceros software. As a result of the experiments, it has been determined that cracks occur in dry areas and veins on the slabs. In these first trial productions, the targeted quality could not be achieved. Therefore, in order to solve the surface problems, it was determined that the consistency between base and vein was crucial and base and vein formulation studies were continued.

In addition, an additional robotic arm (Roy Mix) was added next to the current robotic arm in order to achieve the thick vein appearance of the original Calacatta marble. The vein discarded from Roy Mix is called "wet mixture". Furthermore, the viscosity of the wet mixture discarded from Roy Mix's chamber can be formed with similar viscosity of the base. In order to overcome the dryness and surface defects of the stones produced by using dry mixture formed in the laboratory, formulas of wet mixture close to the viscosity of the base were formed. In addition, the base resin rate was increased in the range of 1-10% for better wetting of the base. In order to eliminate the consistency problem between the base and the vein, the edges of the vein were wetted with coloured resin (paste pigment). Besides, it was found that using quartz in the base formula resulted in an opaque and unnatural appearance, while silica sand, quartzite, quartz sand, amorphous quartz, b-Quartz, a-cristobalite, b-cristobalite, a-tridymite, b-tridymite, milky quartz, transparent quartz were found to work better and give a more natural appearance. For this reason, the appearance of Calacatta marble was obtained by working on a cristobalite base. Natural Calacatta marble samples were collected and examined and raw material researches were performed to obtain the vein texture and an appearance similar to that of the original Calacatta marble surface. The usability of raw materials in the vibratory compaction method under vacuum was investigated and the technical formulas studies of the base were performed with the selected raw materials. Then, these formulas were tested in the pilot facility. The resistance tests of the slabs obtained as a result of the tests were carried out in the final product control test laboratory. As the base formula outputs pass the standard tests, the vein formula was obtained to give the original Calacatta marble texture. Since the viscosity properties of the vein formula will work in the base formula, its compatibility with the base formula was examined. Technical formulation studies for the vein were carried out in this regard. Methods were established in the pilot facility to be used in production. Methods and tests were developed for the physical opening of channels and filling them with vein according to the viscosity properties of the base formula. Shapes of the channels, the thickness of the channels, the design of the apparatus and jugs that can open channels were investigated to form the veins. Experiments were conducted at the pilot facility with the jags of these channel opener apparatus and studies were carried out to determine the fluidity of the vein formula to fill the channels according to the shape and colour of the designed veins. For this purpose, the effect of formula compliance of the base and vein on the quartz surface was examined. The formation and curing of the with two different formulas were examined under the press and the matrix surface produced by both s was examined during the curing process. In addition, reaction times were measured by applying exothermic reaction on vein and base. Problems that may occur in curing together were investigated when they exhibited different reaction times. Studies on the waiting time of the base formula started during the vein formation. As a result, in case of prolongation of the process, the base formula was semi-cured and it was examined whether the vein had finished filling and fusing with the main formula before it became dull and arrangements were made in the method. For each Calacatta marble-like product to be designed, these processes were repeated separately, and statistical data were created to examine the accuracy of the process. The vein shapes on marble, which is a natural stone, can be very thick, very thin, very dense or very little. Finally, the effect of calibrating, polishing, and cutting properties on cured samples was examined.

Activities carried out within the scope of experimental studies:

Calacatta marble samples were examined within the scope of experimental studies. In order to obtain the texture and color of the original marble base, interviews were made with raw material producers.

A quartz work was requested from raw material suppliers to obtain marble whiteness with colour values of L=85-99; a=0.05-0,5; b=l-3 for size 100-40 and the filling material as L=85-99; a=0.05-0,5; b=l-3 for 38 pm size. After the grain size of the incoming samples was verified on the sieve vibration machine, colour measurements were performed.

A step was taken towards the method determination phase at the prototype plant with the incoming raw materials and the formulation studies were started. A total of eight base formulations were created: namely Base-1, Base-2, Base-3, Base-4, Base-5, Base-6, Base-7, and Base-8.

Base formulation samples (Base-1, Base-2, Base-3, Base-4, Base-5, Base-6, Base-7, and Base-8) which were formed in the laboratory and consisted of quartz and / or silica sand and / or quartzite and / or quartz sand and / or amorphous quartz and / or b-quartz and / or a-cristobalite and / or b-cristobalite and / or a- tridymite and / or b-tridymite and / or milky quartz and / or transparent quartz 45 pm in size at the rate of 20 - 40% by weight and 100 - 400 pm in size at the rate of 60-80 % by weight, respectively, plus resin at the rate of 6-26% by weight were tested mechanically. Bending Resistance, Impact Resistance, Abrasion Resistance and Water Absorption Rates were measured (Table 1). Table 1. Prototype mechanical test results

*B: Base formula After the base formula was created, vein formula studies were started to provide the original marble texture. The veins in Calacatta marble have a thick structure. Large areas must be opened and filled in order to obtain thick veins on the product. Hence, the vein should be prepared as a mixture consisting of only quartz and pigment is not sufficient. Under normal conditions, the to be prepared with the same properties as the product's own base will provide maximum compliance and minimum error. However, the vein paths to be opened in the appearance of natural marble in the base were again filled with a robotic arm and it was found in the studies that with the same viscosity of the base would not be fluid. For this reason, a special that can be used with the robot arm has been formulated. Furthermore, in the prototype facility, vein formulations were developed consisting of quartz and / or silica sand and / or quartzite and / or quartz sand and / or amorphous quartz and / or b-quartz and / or a-cristobalite and / or b-cristobalite and / or a-tridymite and / or b-tridymite and / or milky quartz and / or transparent quartz 45 pm in size at the rate of %20-40 % by weight and 100- 400 pm in size at the rate of %60-80, respectively, plus resin at the rate of 6-26% by weight.

Formulation studies have been performed with different proportions of resin, micronized quartz, and granular quartz. Formation studies were performed with quartz, silica sand, quartzite, quartz sand, amorphous quartz, b-Quartz, a- cristobalite, b-cristobalite, a-tridymite, b-tridymite, milky quartz, transparent quartz raw materials in order to obtain the appearance of Calacatta marble. Iron oxide, titanium dioxide, copper chromium oxide, carbon black, manganese iron oxide (spinel and hematite structure), chromium iron oxide (hematite structure) pigments were used in the formulation in order to obtain the vein colours of Calacatta marble in quartz formulations with different properties. Thanks to the pigments used, all colours between white and black were obtained on the colour scale. The formulation was named as "dry mixture". In the dry mixture application, the channels opened on the basis of the product are filled with vein wetted with resin spray and the filled is wetted again by spraying resin.

The viscosity of the standard resin used in production is in the range of 500-700 cp. A lower viscosity resin was required to apply the resin with the robot. For this reason, the viscosity of the resin was reduced to 50-150 Cp by adding styrene monomer at the rate of 5-40% by weight into the unsaturated polyester resin.

After the base and vein formulations were created in the prototype, vein maps with Carrara Marble appearance were drawn using Rhinoceros program.

Operational tests of base and formulas created in the prototype laboratory with the drawn vein maps were performed with a robotic arm. Forming and curing processes of two different types of formula by pressing were examined and it was evaluated whether there were cracks and dryness on the surface. In addition, mechanical tests of the formulas were performed (Table 2).

Table 2. Operational test mechanical test results