CA2590599C - Artificial stone molded product - Google Patents
Artificial stone molded product Download PDFInfo
- Publication number
- CA2590599C CA2590599C CA002590599A CA2590599A CA2590599C CA 2590599 C CA2590599 C CA 2590599C CA 002590599 A CA002590599 A CA 002590599A CA 2590599 A CA2590599 A CA 2590599A CA 2590599 C CA2590599 C CA 2590599C
- Authority
- CA
- Canada
- Prior art keywords
- aggregate
- inorganic material
- molded product
- luminous
- artificial stone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002969 artificial stone Substances 0.000 title claims abstract description 76
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 238000010521 absorption reaction Methods 0.000 claims abstract description 13
- 229910010272 inorganic material Inorganic materials 0.000 claims description 77
- 239000011147 inorganic material Substances 0.000 claims description 77
- 239000000463 material Substances 0.000 claims description 64
- 239000000843 powder Substances 0.000 claims description 55
- 239000011347 resin Substances 0.000 claims description 45
- 229920005989 resin Polymers 0.000 claims description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000465 moulding Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 238000004020 luminiscence type Methods 0.000 claims description 12
- 239000011435 rock Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 6
- 239000000113 methacrylic resin Substances 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 6
- 239000011707 mineral Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 66
- 239000002245 particle Substances 0.000 description 16
- 238000005498 polishing Methods 0.000 description 12
- 238000005299 abrasion Methods 0.000 description 11
- 239000004575 stone Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000005084 Strontium aluminate Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000032798 delamination Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010438 granite Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 chrysolite Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000004579 marble Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- CUARLQDWYSRQDF-UHFFFAOYSA-N 5-Nitroacenaphthene Chemical compound C1CC2=CC=CC3=C2C1=CC=C3[N+](=O)[O-] CUARLQDWYSRQDF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 241001207849 Canis anthus Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 241000613130 Tima Species 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052611 pyroxene Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000010458 rotten stone Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
- B29C70/585—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres incorporation of light reflecting filler, e.g. lamellae to obtain pearlescent effet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44F—SPECIAL DESIGNS OR PICTURES
- B44F9/00—Designs imitating natural patterns
- B44F9/04—Designs imitating natural patterns of stone surfaces, e.g. marble
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Finishing Walls (AREA)
- Road Paving Structures (AREA)
Abstract
A formed artificial stone (1) having integrally on a flat surface portion of a substrate (2) thereof projecting portions (3) for forming graphics or patterns or embedded groove portions (4) and mainly formed as a main composition from mineral aggregates andresin, characterized in that at least a part of the projecting portion (3) or the embedded groove portion (4) is a luminous or fluorescent illuminating portion and that this illuminating portion contains as at least a part of the mineral aggregate a luminous or fluorescent substance having a luminous property or an illuminating property due to the absorption of ultraviolet rays and a transparent mineral aggregate, or a transparent mineral aggregate having the luminous or fluorescent substance stoved on the surface thereof.
Description
ARTIFICIAL STONE MOLDED PRODUCT
TECHNICAL FIELD
The invention of the present application relates to an artificial stone molded product. More specifically, the invention of the present application relates to an artificial stone molded product which has a night decorativeness, a luminousness such as a luminescence and a light-emitting property acccwnpanied by ultraviolet absorption and which is useful in a building material or a sight material as a direction indicator or a position guide using light in dark surroundings.
BACKGROUND ART
An artificial stone obtained by pulverizing a natural stone and mixing the pulverizate with a resin or the like for solidification has boon so far known. And regarding this artificial stone, various atternpts have been made to provide a product having a tons of a natural stone such as marble, granite or the like and being excellent in a hardness and a strength.
As an approach to improve properties and a performance of such an artificial stone, there has been also a proposal of imparting a light function using a luminous material such as a luminescent material or a fluorescent material such as an ultraviolet light-emitting material which e:nits light through ultraviolet absorption. This approach is conducted by mixing a fluorescent material with a resin component as a binder of an artificial stone for solidification or by nni.xing a luminescent fluorescent material such as strontium aluminate or the like or a ultraviolet fluorescent material with an unsaturated polyester, a methacrylic resin, a glass or the like for solidification, pulverizing the mixtura, and using the resulting product as an aggregate to form an artificial stone.
TECHNICAL FIELD
The invention of the present application relates to an artificial stone molded product. More specifically, the invention of the present application relates to an artificial stone molded product which has a night decorativeness, a luminousness such as a luminescence and a light-emitting property acccwnpanied by ultraviolet absorption and which is useful in a building material or a sight material as a direction indicator or a position guide using light in dark surroundings.
BACKGROUND ART
An artificial stone obtained by pulverizing a natural stone and mixing the pulverizate with a resin or the like for solidification has boon so far known. And regarding this artificial stone, various atternpts have been made to provide a product having a tons of a natural stone such as marble, granite or the like and being excellent in a hardness and a strength.
As an approach to improve properties and a performance of such an artificial stone, there has been also a proposal of imparting a light function using a luminous material such as a luminescent material or a fluorescent material such as an ultraviolet light-emitting material which e:nits light through ultraviolet absorption. This approach is conducted by mixing a fluorescent material with a resin component as a binder of an artificial stone for solidification or by nni.xing a luminescent fluorescent material such as strontium aluminate or the like or a ultraviolet fluorescent material with an unsaturated polyester, a methacrylic resin, a glass or the like for solidification, pulverizing the mixtura, and using the resulting product as an aggregate to form an artificial stone.
However, in the case of the conventional luminous or fluorescent artificial stone, there were defects that in either of the above-mentioned methods, it is only in the position where the binder resin component or the aggregate exposed to the surface of the artificial stone is arranged that the luminescent material or the like gives the fluorescent function and the luminescent material or the like contained in the artificial stone molded product does not act at all in portions other than the above-mentioned. A fluorescent material such as a luminescent material or the like is quite expensive, and even the addition of the same in a small amount increases the overall cost to from 3 to 10 timas.
Accordingly, the ordinary artificial stone containing therein a fluorescent material free from this function was not practical in view of the cost.
Further, a luminous layer formed of a luminesc nt material on a surface of an artificial stone has been so far mostly spread throughout the surface. Accordingly, for example, a product is not one in which only a guide figure or a guide pattern indicating a direction or a position which is required in dark surroundings at night is formed of a luminous layer.
Meanwhile, it has also been studied that only a gvide figure or a guide pattern is formed of a luminous layer as mentioned above.
However, in the casw of the ordinary luminous layer, an adhesion with a substrate is poor, and the luminous layer itself has a poor abrasion resistance. Accordingly, there has been a problem that especially in the application to a floor, a predetermined function is not provided owing to delamination, dropping, abrasion and the like of the luminous layer.
For this reason, there have been so far problems that the application and the design of the luminous artificial stone are quite limited owing to a high cost and restrictions of a luminousness and physical properties.
Accordingly, the ordinary artificial stone containing therein a fluorescent material free from this function was not practical in view of the cost.
Further, a luminous layer formed of a luminesc nt material on a surface of an artificial stone has been so far mostly spread throughout the surface. Accordingly, for example, a product is not one in which only a guide figure or a guide pattern indicating a direction or a position which is required in dark surroundings at night is formed of a luminous layer.
Meanwhile, it has also been studied that only a gvide figure or a guide pattern is formed of a luminous layer as mentioned above.
However, in the casw of the ordinary luminous layer, an adhesion with a substrate is poor, and the luminous layer itself has a poor abrasion resistance. Accordingly, there has been a problem that especially in the application to a floor, a predetermined function is not provided owing to delamination, dropping, abrasion and the like of the luminous layer.
For this reason, there have been so far problems that the application and the design of the luminous artificial stone are quite limited owing to a high cost and restrictions of a luminousness and physical properties.
It has been therefore required to realize a new artificial stone molded product which is excellent in a luminousness as well as in an adhesion integrity with a substrate of a luminous layer and physical properties such as an abrasion resistance and the like, which has a luminousness or a fluorescence and which is useful as a light guide or a night decorative material in dark surroundinqs, while decreasing the cost of the product upon using a luminous or fluorescent material such as a lumincscont material or the like only in a figure or a pattern required.
DISCLOSURE OF INVENTION
In order to solve the above-mentioned problems, the invention of the present application provides an artificial stone molded product in which protrusions or embedded grooves for a fiqure or a pattern are provided integrally on or in a flat surface of a substrate, and a main composition comprises an aggregate of an inorganic material and a resin, characterized in that at least a part of the above-mentioned protrusions or eubedded grooves are luminous or fluorescent light-emitting portions which contain a luminous or fluorescent material having a luminescence or a luminousness accompanied by ultraviolet absorption and an aggregate of a transparent inorganic material, or an aggregate of a transparent inorganic material having a surface baked with the above-mentioned luminous or fluorescent material as a part of the aggregate of the inorganic material.
The present invontion further provides a process for producing the above-mentioned artificial stone molded product.
BRIEF DESCRIPTION OF THE DRAWINGS
Figures 1 and 2 of the drawings attached are each a sectional view showing a structure of an artificial stone in the present invention.
DISCLOSURE OF INVENTION
In order to solve the above-mentioned problems, the invention of the present application provides an artificial stone molded product in which protrusions or embedded grooves for a fiqure or a pattern are provided integrally on or in a flat surface of a substrate, and a main composition comprises an aggregate of an inorganic material and a resin, characterized in that at least a part of the above-mentioned protrusions or eubedded grooves are luminous or fluorescent light-emitting portions which contain a luminous or fluorescent material having a luminescence or a luminousness accompanied by ultraviolet absorption and an aggregate of a transparent inorganic material, or an aggregate of a transparent inorganic material having a surface baked with the above-mentioned luminous or fluorescent material as a part of the aggregate of the inorganic material.
The present invontion further provides a process for producing the above-mentioned artificial stone molded product.
BRIEF DESCRIPTION OF THE DRAWINGS
Figures 1 and 2 of the drawings attached are each a sectional view showing a structure of an artificial stone in the present invention.
Figures 3 and 4 are each a flow chart of a process for producing the same in the present invention.
BEST MOOE FOR CARRYING OUT THE INVENTION
The invention of the present application is described in more detail below.
The artificial stone molded product intended by the present invention can be described by referring to, for example, Figures 1 and 2 of the drawings. In the case of Figure 1, an artificial stone molded product (1) has protrusions (3) on a flat surface of a substrate (2) , and the protrusions (3) are arranged and formed to give a predetermined figure or pattern. And this protrusion (3) is a luminous or fluorescent light-emitting portion having a luminescence or a luminousness accompanied by ultraviolet absorption. The substrate (2) itself does not form such a light-emitting portion.
Zn the case of Figure 2, the substrate (2) is provided with embedded grooves (4) having embedded therein light-emitting portions.
The protrusion (3) as light-emitting portions, as shown in Figure 1, can have, for example, a function of a braille block in the daytime and a function of a mark for a guide of a direction or a position in dark surroundings at night. In the case of Figure 2, it is likewise useful as a mark for a guide. Of course, a decoration at night or the like can also be provided.
As stated above, it is an objQct of the present invcntion that only the protrusions (3) and the embedded grooves (4) can selectively become light-emitting portions. In the conventional art, this was quite difficult. It was largely because the adhesion integrity between the substrate and the light-emitting portions is poor and the light-emitting portions themselves have a poor abrasion resiatancg.
The present invention is to provide, upon conquerinq such defects of the conventional art, an artificial stone molded product which enables the cost to dscrease by the selective formation of light-eini.ttin9 portions and which prQvonts delamination, dropping and abrasion.
With respect to the composition of the artificial stone, in the present invention, it contains an aggregate of an inorganic material and a resin as basic romponents in the substrate (2), the protrusions (3) and also the embedded grooves (4) in Figures 1 and 2. In this instance, the aggregate of the inorganic material includes a wide variety of materials such as a natural stone, a natural mineral, a synthetic inorganicmaterial, a glass, a metal and the like.
And what is important in the present invention is that a luminous or fluorescent material and an aggregate of a transparent inorganic material or an aggregate of a transparent inorganic material having a surface layer coated with a luminous or fluorescent material is contained in at least a part of tho aggregate of the inorganic material in the light-emitting portions constituting the above-mentioned protrusions (3) or the embedded grooves (4).
When the light-emitting portion contains the aggregate of the transparent inorganic material along with the lumtiinous or fluorescent material, it is indispensable that the weight ratio of both materials is between 1:2 and 1:10 and the sum of both materials is between 80 and 95% by weight based on the overall composition of the light-emitting portion.
Further, when the light-emitting portion contains the aggregate of the transparent inorganic material having the surface coated with the luminous or fluorescent material, it is indispensable that the weight ratio of this material is between S and 65% by weight based on the overall composition of the.
light-emitting portion.
The above-mentioned requirements are defined in view of physical properties such as a delamination resistance, a drop resistance, an abrasion resistands and the like, and a luminousness.
As the aggregate of the inorganic material, a combination of the following two types is preferable. That is, one is a fine powder component of an inorganic material having a size of from to 70 mwsh. This is a fine powder component of an appropriate inorganic material selected from minerals such as silica, rocK, chrysolite, feldspar, pyroxene, mica and the like, natural stones such as granite, metamorphite and the lika, porcelain, glasses, metals and the like.
And along with this fine powder component, a finely divided coa-ponent having a size of 100 mesh-under is preferably used. As this finely divided component, various natural or artificial finely divided components are mentioned. For example, powders of calcium carbonate, aluminum hydroxido and silica rock are easily obtainable finely divided components.
Flsrther, as a part of this finely divided coisqnonent, a component such as manganese dioxide, titanium dioxide, zirconium silicate, iron oxide or the like to adjust a color tone, or a component such as antimony trioxide (pentoxide) , a boron compound, a bromine compound or the like to impart a flame ratardance and an incombustibility may be blended.
The above-mentioned fine powder component acts as a main factor of an appearance and physical properties of the resulting artificial stone molded product. The size of the finely divided component is much smaller than the 100 mesh level in comparison to the fine powder component. The finely divided component enters between the individual particles of the fine powder component and is arranged to fill the space between the particles, contributinQ toward providing propertiea such as a hardness and a pliability of the resultting artificial stone. The weight ratio of the fine powder component and the finely divided component is preferably between 0. 5:1 and 5:1, more preferably bQtwoen 1:1 and 4:1. A'hen the artificial stone molded article of the present invention is formed of a cocnbination of the fine powder component and the finely divided corRponent, the structure of the light-emitting portion Can be considered as follows.
<A> When the luminous or fluorescent material and the aggregate of the transparent inorganic material are used as a part of the aggregate of the inorganic material, it is advisable that the component of the transparent inorganic material is usec3.as at least a part of the fine powder component and the luminous or fluorescent tttztsrial is used as at least a part of the finely divided component.
The fine powder cotnponent as the aggregate of the transparent inorganic material refers to a coniponent of an inorganic material having substantially a high light transmission. The transparency thereof includes various degrees.
A natural or synthetic inorganic material having a relatively high light transmission is to be used in the present invention.
Consequently, the fine powder consponent.of the transparent inorganic material may be colored or have a peculiar color.
Quartz, silica rock, a glass and the like are typically mentioned in the present invention as the fine powder component of the transparant inorganic material. However, it is not limited thereto.
And the artificial stone taolded product of the present inventi.on contains, as a part of the finely divided component, a luminous or fluorescent ccnWnent'having a luminescence or a luminousness accompanied by ultraviolet absorption and having a size of 100 mesh-under. Typical axacnplas of such a component e include a strontium aluminate ltani.nescent material, zinc sulfide and the like. These materials are used in, the present invention.
The fine powder component of the inorganic material which plays a roll as an aggregate of an artificial stone haa a size of from 5 to 70 mash as mentioned above, and this is an indispensable requirement in the combination with the finely divided component of the inorganic material. And the above-mentioned luminous or fluorescent component plays the same roll as the finely divided coMponent, and imparts the light function such as the luminousness or the fluorescence to the artificial stone. It is also indispensable that the size of the luminous or fluorescent component is 100 mash-under as in the finely divided component.
With respect to each of the above-mentioned components of the inorganic materials, the mixing ratio is an important requirement along with its size.
That is, in the aomposition of the artificial stone of t:5e present invention, the, relationship of the weight (W1) of the above-mentioned fine powder ccsnponent of the inorganic material, the weight (Ws) of the finely divided component of the inorganic material and the weight (Ws) of the luminous or fluorescent component is preferably as follows.
Wi : (W=+F1,) =0.5:1 to5:1 W2 : W3 = 1:2 to 10:1 With respect to Wi :(Ws + p,) , it is preferably between 1:1 and 4:1. With respect to WZ : W,, it is preferably betwoen 1:1 and 5:1.
And in the fine powder component of the inorganic material, as mentioned,above, it is advisable that the ratio of the fine powder component of the transparent inorganic material therein has preferably the following relationship (0.5 to 1.0)W=.
The above-mAntioned facts aro required to realize physical properties as an artificial stone, such as a strength, a hardness, a density and the like, and a light function such as a luminousness or a fluorescence.
Specifically, the size of each component is selected, as required, depending on a size and a mixing ratio of each component used in combination. Generally, it is preferable that the size of the finely divided component and the luminous or fluorescent component is between 150 and 250 mesh.
The light function of the artificial stone is further described. With respect to the artificial stone of the present invention, the light function of the luminous or fluorescent artificial stone is realized in such a manner that 1) from 30 to 100% by weight of the fine powder component of the inorganic material is a fine powdar of a transparent inorganic material, and 2) a luminous or fluorescp-nt component of 100 zswsh-under is mixed at the above-mantioned specific ratio. And the characteristic feature in this case is that light can be emitted as light having a thickness. It is not that light is emitted in the surface layer alone as in the prior art, but that light is emitted in the overall thickness of an artificial stone. Thus, the product is excellent in the luminousness and the economics in view of the use of an expensive luminous or fluorescent component.
The reason is aa follows. The use of the fine powder componpnt of the transparent inorganic material as a traneparent aggregate permeates light emitted from outside into the inside of the artificial stone to efficiently absorb the light energy in the luminous or fluorescent component, and the lulninous layer having dispersed therein the luminous or fluorescent component formed of the luminescent material or the like is secured as a great thickness including the inside of the artificial stone, so that a high luminosity can be maintained for a long period of time.
In the light emission, the fine powder component of the transparent inorganic material coer-as to have a high luminosity because it is good in a light transmission.
The ratio of the transparent component occupied in the overall fine powder component is, as mentioned above, between 30 and 100$ by weight. Naturally, in some physical properties of an artificial stone, such as a strangth and the like and some external design, a ratio of 100% is preferable from the standpoint of a light function. Of course, this is not critical. However, when it is iess than 3U% by weight, a desired light function is hardly provided.
<B> When the aggregate of the trs.nsparent inorganic material having the surface baked with the luminous or fluorescent material is used as a part of the aggregate of the inorganic material, it can be used such that at least a part of the fine powder component is transparent, and it has the surface baked with the luminous macerial having a luminescence or the like or the fluorescent material having a luminousness accompanied by ultraviolet absorption. That is, a part or the whole of the fine powder component is the aggregate of the transparent inorganic material having the surface coated with the luminous material or the fluorescent material. Appropriate examples of such an aggregate of the inorganic material having the transparent light include a glass, silica rock and the like.
Regarding the fine powder component incorporated in the coraposition, it is advisable that the ratio (weight) of from 10 to 100% is used in the above-mentioned aggregate of the transparent inorganic material having the surface layer coated with the above-mentioned luminous or fluorescent material.
In the aggregate of the transparent inorganic material, ospecially, the baked coating of the fine powder component, a coating having a thickness of from several-iaicrometers to several tens of mierometers, for example, from S to 50 m, preferably from 20 to 40 (.un is applied to the surface of the particle in the transparent fine powder componant. More specifically,.the coating is applied by the baking at a high temperature of from 120 to 1,200 C.
The fluorescent material to be baked can include various fluorescent materials which have a luminescence or which emit light through ultraviolet-light irradiation, such as strontium aluminate, zinc sulfide and the like.
The baking is conducted not by various known methods, but by mixing the aggregate of the transparent inorganic material, for example, the above-mentioned fine powder component with a dispersion or a paste having dispersed therein a fine powder of a luminescent material such as strontium aluminate or the like and drying the mixture.
In the present invention, it is advisable that the fine powder component of the inorganic material has the specific size as noted above. That is, the fine powder component of the inorganic material has a size of from 5 to 70 mssh as mentioned above. When an upper or lower portion is colored dark using the colored and colorless materials, it is considered that the size of fine particles is changed depending on the colored or colorless condition. However, fine particles which are extremely different in the size shall not be used in large amounts because they deteriorate the strength of the product.
Meanwhile, the size of particles of the finely divided cemponent is 100 mesh-under as noted above. The particles of the finely divided component have to be fully incorporated between the particles of the fine powder cornponent. More specifically, the size ia preferably between 150 and 250 mesh.
And what is ing>ortant in the high-density artificial stone of the present invention is that the aggregate components of these inorganic materials are preferably dispersed uniformly in any portions of the product except in special cases.
E~rther, the resin component can be selected from a wide variety of thermosetting materials_ For example, an acrylic resin, a methacrylic resin and an unsaturated polyester resin are mentioned. Of these, the methaerylie resin is preferable in view of a transparency, a hardness, a strength and the like. The ratio of the resin component is proferably less than 15% by weight, further preferably 10% by waight or less basad on the total composition.
This resin component contributes to covering the fine powder component and the finely divided component which are components forming the above-mentti.oned structure to bind the whole body, and functions to impart a resilience or a tensile strength to a product when an artificial stone is completad. Tha ratio of the aggregate of the inorganic material formed of the fine powder component and the finely divided ecxmponent is limited. That is, it has to be 85$ by weight or more, preferably 89% by weight or more. When it exceeds 95$, the product becomes brittle and is hard to use.
When it is less than 85%, the product becomes too soft to give qualities as a stone. Thus, the product is used in the same range as a resin plate.
This means that the component other than the fine powder cornponent and the finely divided component such as a natural stone and the like, namely, the resin component should not be present in the product in an amount exceeding 15.1 by weight.
When the amount of the resin component exceeds 15%, the product is like plastics, and it is only seemingly an artificial stone. Further, when the amount of the resin component is excessively decreased, a product comes to have an appearance close to a natural color, but it becomes brittls and is unsuitable for actual use. From this standpoint, the amount of the resin component is more preferably between 5 and 11% by weight.
In practicing the present invention, the ratios of thoa components are important. Especially important is a ratio of the resin component to the other component. In the present invention, one of the characteristic features is that a high-density product having a dense texture can be providad. The high density here raferred to means that the fine powder component and the finely divided component contained in the artificial stone product are present in a high density. For exwple, this density ia 2.2 g/an' or more which exceeds the range in the conventional artificial s tone .
It is advisable that the outer surface of the product is polished or roughened. In practice, it is preferable that the broken fine powder component is exposed.
The polishing is a practically convenient method for exposing the dense texture condition inherent in the high-density artificial stone having a deep atmosphere in the present invention.
It is, of course, possible that a part of a surface of a product is polished to expose the fine powder cornponent and a difference with another portion in the same surface is used as a pattern.
Further, when an artificial stone is obtained, it is an important problem what a desired color or design is. Granite or marble is one goal because.a product formed of a natural stone is hardly obtained and a color and a glaze thereof aro beautiful.
In the present invention, the transparent component is used as the fine powder component, making it possible to obtain a product having a glaze of granite, marble or the like. This is because a fine powder obtained by pulverizing a quartz-type natural stone is used as the fine powder component.
The fine powder obtained by pulverizing the quartz-type natural stone is colorless and transparent in many cases. In a non-transparent powder, a transparent often remains slightly.
It is also possible to provide a uniform color and a deep, glazed peculiar tone of color by adding an inorganic pigment, an organic pigment such as an azo pigment or a phthalocyanine pigmant, or various dyes.
In the composition of the artificial stone in the present invention, the product can also be colored by using colored particles having the same size as tho fine powder component, an a color component.
In any case, the color reproducibility can be secured quite easily in comparison to the conventional artificial stono, and a product which is axcellent in a dept and a.Qlaze without discoloration can be obtained.
The high-density artificial stone of the present invention having usually excellent color tone characteristics along with a luminescence, a ultraviolet light-emitting property and the like can have any form, examples of the form being a plate, a bar, a cylinder and the like.
The above-mentioned artificial stone molded product of the prasent invention can be produced by, for example, the following process.
<I> Molded product in which protrusions are light-emitting portions:
Fiqure 3 is a flow chart showing a typical process for producing an artificial stone molded product (1) in which protrusions (3) are light-emitting portions.
That is, this Figure 3 shows a process for producing an artificial stone molded prvduct in which protrusions (3) for a figure or a pattern are integrally provided on a flat surface of a substrate (2) , a main composition comprises an aggregate of an inorganic material and a resin, and at least a part of the protrusions (3) are luminous or fluorescent light-emitting portions, which comprises injecting a mixture (6) for resin molding containing a luminous or fluorescent material having a luminescance or a luminousness accompanied by ultraviolet absorption and an aggregate of a transparent inorganic material or an aggregate of a transparent inorganic material having a surface baked with the luminous or fluorescent material as at least a part of the aggregate of the inorganic material into grooves (51) of a mold (5) which correspond to the protrusions (3) of the molded product and which are formed in the inner bottom surface, then injecting a mixture (7) for resin molding containing an aggregate of an inorganic material into the mold (5), preaa-curing the mixture, withdrawing the product from the mold, and further polishing the product or roughening the product using a water jet or the like as required to produce an artificial stone molded product (1) having light-emitting portions in the protrusions (3) alone.
In the curing upon fitting a male mold (8) , the compression is conducted by pressing with a surface pressure of, for examle, from 5 to 100 kgf/ccm2. In this molding, heating is conducted at a temperature of from approximately 90 to 140 C for from 5 to 20 minutes in tha compression.
Tha mixture (6) for resin molding which forms the light-esnitting portions as the protrusions (3) and the mixture (7) for resin molding which forms the substrate (2) are integrally molded in the above-mentioned curing step by the compression.
Accordingly, delamination or dropping of the light-emitting protrusions (3) does not occur. Besides, the protrusions (3) are also formed as having an excellent abrasion resiatance due to its cornposi tion .
This process using such a cotnpression molding exhibits a i6 mass-production effect as a process for produc.ing a product with a relatively simple shape, such as a flat molded product, and there is almost no loss of a material, so that this process is economically excellent too.
A means for surface polishing is not particularly limited.
It can be conducted using a tool such as a grindstone, a polishing cloth, a polishing belt or the like, or a polishing agent such as a buff polishing agent, a rubbing compound or the like.
As the polishing agent, diamond, boron carbide, corundum, alumina and zirconia which have mainly a polishing action, and tripoli, dromite, alumina, chromium oxide and cerium oxide which have mainly a scratching action are used as required.
And in the present invQntion, the surface of the molded product after the molding may be roughened to expose the finely divided couponent to the 'surface portion.
To this end, a method of selectively removing the rosin component is employed. That is, it is effective; for example, that after the product is removed from the mold, high-pressure water is jetted on the surface of the molded product to conduct the texture treatment.
Since this treatment varies dependtng on various conditions such as a thickness, a distance from a nozzle, a treatment mode and the like, it is not limitative. However, usually, in the case of a thickness of from 2 to 20 ean, a water pressure of from 50 to 1,400 kg/czn= can be applied from a height of a noz2lo of froen 2 to 50 cra. This water pres9ura is far lower than when a natural stone is used.
That is, this is because the high-quality treatment can be conducted more easily by the presence of a rosin coanponont.
A nozzle for jetting high-pressure water or its system is not particularly limited. Various types are employable.
The surface is flattened or roughened using the water jet in the texture treatment to produce an artificial stone having a deep quality.
The presence of the resin component does not make the surface cloudy, and makes easy the treatment of a waste wster in comparison to an etching method using chemicals.
Naturally, the surface can be treated with an organic solvent as required to soften or melt the resin component and partially remove the same.
In this case, the organic solvent correaponding to the resin component may be selected. Examples thereof include halogenated hydrocarbons such as methylene chloride and chloroform, carboxylic acids and esters thereof such as acetic anhydride, ethyl acetate and butyl acetate, acetone, tatrahydrofuran, DMF
and DM30.
The molded product is dipped in these orQanic solvents or these organic solvents are sprayed thereon or caused to flow down thereon to remove the resin component softened or melted from the surface whereby the uneven surface can be formed.
Alternatively, the uneven surface may be formed by scratching the resin component having a low hardness from the surface with a wire brush, a cutting means or the like.
The surface is xoughonoddby the above-mentioned various means, and the texture is treated. Then, the resulting surface is polished as noted above to realize the peculiar deep, glazed surface.
<II> Molded product in which embedded grooves are light-emitting portions:
Figure 4 is a flow chart showing a typical process for producing an artificial stone molded product (1) in which embodded grooves (4) are light-emitting portions.
That is, this Figure 4 shows a process for producing an artificial stone molded product in which aenbedded grooves (4) for a figure or a pattern are integrally provided in a flat surface of a substrate (2 ), a main composi tion comprises an aggregate of an inorganic material and a resin, and luminous or fluorescent light-emitting portions are embedded in at least a part of the embedded grooves (4), which comprisas injecting a mixture (7) for resin molding containing an aggregate of an inorganic material into a mold (5) having protrusions (52) corresponding to the meibedr3ed grooves (4) of the molded product in the inner bottom surface, curing or half-curing the mixture, withdrawing the resulting product from the mold, injecting a mixture (6) for resin molding containing a luminous or fluorescent ma.terial having a luminescence or a luminousness accompanied by ultraviolet absorption and an aggregate of a transparent inorganic material or an aggregate of a transparent inorganic material having a surface baked with the luminous or fluorescent material as at ieast a part of the aggregate of the inorganic material into grooves formed in the surface of the molded product to produce an artificial stone molded product (1) having the light-anitting portions in the embedded grooves (4) alone.
In this process as well, the curing by compression molding can be conducted in the above-mentioned manner, and the surface of the molded product (1) ie likewise finally polished or roughened as required. The mixtures (6) ,(7) for resin molding are also integrated.
For example, when the aggregate of the transparent inorganic material having the surface coated with the luminous or fluorescent material is used as the mixture (6) for resin molding in either process, the soctions of the particles and the coating layer are exposed by treatment such'as polishing or the like.
In this manner also, an artificial stone which is excellent in light-emitting characteristics, a texture and qualities is produced.
That is, for example, when a luminescent or ultraviolet light-emitting material is baked and coated on the surface of the fine powder component, the particles of the fine powder component and the coating thereof are exposed as sections by polishing the surface of the artificial stone. Consequently, light irradiated from outside is entered frosn the exposed particle surface of thA
transparent fine powder and reaches the baked coating material in the inside.
In the case of a highly transparent methacrylic resin or the like, the light transmission is rendered wholly good.
For this reason, incident light ss transmitted into the inside of the light-emitting portion, and light is also emitted from inside.
Accordingly, light can be stored in a short period of time, and a light-emitting efficiency is also increased.
The present invention is illustrated by referring to the following Examples. Naturally, the present invention is not limited to the following Exaunples.
EXAMPLE
Example 1 An artificial stone molded product was produced according to a process shown in Figure 3.
That is, a mixture (6) for resin mOlding having the following fozinulation was injected into grooves (51) having a depth of 6 rrm in a mold (5).
Silica rock of from 10 to 50 mesh in which 60% by weight a surface layer baked with a strontium aluminate luminescent material at approximately 11000 C was formed to a thickness of approximately 30 pm Silica rock powder having an average 30% by weight particle diameter of 250 mesh Methyl methacrylate (MM) (containing 10% by weight 0.15$ of a peroxide-type curing agent) Subsequently, a mixture (7) for resin molding having tha following formulation was injected into the mold (5).
Silica rock of from 10 to 70 mesh 20-t by weight Silica rock of from 10 to 70 mesh having 42% by weight on tho surface a baked layer of a yellow pigment with a thickness of 30 rn Aluminum oxide powder having an average 30$ by weight particle diameter of 225 mesh Methyl mathacrylate (Hmk) (containing 8$ by weight 0.15% of a peroxide-type curing agent) An upper mold (8) was placed theroon, and the mixture was pressed and cured at a temperature of 120 C and a prQSsure of 12 kgf/an2 for 20 minutes.
Then, the product was withdrawn from the mold to obtain an artificial atone molded product (1) in which the thickness of the substrate (2) was 20 nsn and the height of each of the protrusions (3) was 6 mm.
With respect to this molded product (1) , the surface of t.he protrusion (3) was adjusted to a height of 5 nan by polishing the same with a diamond grindstone.
In the resulting molded product (1), the protrusion (3) polished had a light-emitting property such as a luminousness, and exhibited an excellent performance as a position guide mark in dark surroundings. Further, the substrate (2) had an excellent decorativeness as a deep yellow plate, was beautiful even in the daytime and could be used also as a braille block for a blind peraon.
In a test according to JIS K-7112, the apecific gravity was 2.30. Further, the water absorption was 0.14$. With respect to the properties in the protrusions (3) in a region where the substrate (2) and the protrusions (3) were inteqrated, the hardness, the abrasion resistance and the like were excellent as shown in Table 1.
Table 1 item Results Test conditions Sending 63.55 kgf cm aaaordinQ to JI8 A-5209 strength Compression 1380 kgf/cn Crosshead speed 0.5 mm/min strength Load call 2 tons Impact 4,57 kgf=cm/am2 Pendulum impact test strength Hardness 1020 kgf/mn Vickers hardness according to Abrasion 0.01 g J2S A-5209 sand dropping-type rasistance abrasion test Further, no abnormality was observed even in tests for an acid resistance and an alkali resistance by the dipping in a 3*
hydrochloric acid aqueous solution for 8 hours and the dipping in a 3-t sodium hydroxide aqueous solution for 8 hours.
Example 2 The molding was conducted in the same manner as in Example 1, using a mixture (6) for resin molding having the following formulation.
Silica rock of from 10 to 50 mesh in which 50% by weight a surface layer bakod with a strontium aluminate luminescent material at approximately 1,000 C was formed to a thickness of approximately 30 (,tm Silica rock powder having an average 20% by weight particle diameter of 250 mesh Powder of a strontium alesninate 20% by weight luminescent material=having an average particle diameter of 220 mesh Methyl mathacrylate (KIA) (containing 10% by weight 0.2$ by weight of a peroxide-type curing agent) . Th protrusions (3) were polished using a diamond grindstone and a silicon carbide magnosia grindstone. Further, the resin portion alone in the surface portion was removed at a water jet pressure of 1, 200 kg/cm2 (nozzle diameter 0. 8 mm, a jat distance 35 men).
The resulting artificial stone had a depth and a non-slip property in the daytime, and could be seen in the overall thickness direction at night for a long period of time because of the luminescence.
It could be used as a lumi.nous guide mark building material in urgent power failure and thus as an effective artificial stone.
Example 3 The molding was conducted in the same manner as in Example 1, using a mixture (6) for resin molding having the following formulation.
Silica rock of from 10 to 60 mesh 60* by weight Aluminum hydroxide powder having an 22'b by weight average particle diameter of 220 mesh Strontium aluminate luminescent 10-t by weight material havinq an average particle diameter of 200 mesh M~thyl methacrylate (A!MM (containing 8% by weight 0.15'b of a peroxide-type curing agent) Likewise, a molded product which was excellent in physical properties and a luminousness waa obtained.
Example 4 An artificial stone molded product having a thickness of 16 nsn in which embedded, grooves (4) having a depth of 4 rRn were light-em.itting portions was obtained by the process in Figure 4, using the mixtures (6), (7) for resin molding in Exairrple 1.
The surface was polished by means of a diamond grindstone.
A molded product which was excellent in physical properties and a luminousness was obtained.
INDUSTRIAL APPLICABILITY
As stated above, the present invention provides a high-density artificial stone which was excella.nt in light properties such as a luminousness and the like, which had a deep, glazed, excellent tone of color, which was free from problems such as delamination, dropping, abrasion and the like of light-emitting portions and which had good physical properties. Sesides, the production of such an excellAnt product is.realized at far lower costs than the ordinary product.
BEST MOOE FOR CARRYING OUT THE INVENTION
The invention of the present application is described in more detail below.
The artificial stone molded product intended by the present invention can be described by referring to, for example, Figures 1 and 2 of the drawings. In the case of Figure 1, an artificial stone molded product (1) has protrusions (3) on a flat surface of a substrate (2) , and the protrusions (3) are arranged and formed to give a predetermined figure or pattern. And this protrusion (3) is a luminous or fluorescent light-emitting portion having a luminescence or a luminousness accompanied by ultraviolet absorption. The substrate (2) itself does not form such a light-emitting portion.
Zn the case of Figure 2, the substrate (2) is provided with embedded grooves (4) having embedded therein light-emitting portions.
The protrusion (3) as light-emitting portions, as shown in Figure 1, can have, for example, a function of a braille block in the daytime and a function of a mark for a guide of a direction or a position in dark surroundings at night. In the case of Figure 2, it is likewise useful as a mark for a guide. Of course, a decoration at night or the like can also be provided.
As stated above, it is an objQct of the present invcntion that only the protrusions (3) and the embedded grooves (4) can selectively become light-emitting portions. In the conventional art, this was quite difficult. It was largely because the adhesion integrity between the substrate and the light-emitting portions is poor and the light-emitting portions themselves have a poor abrasion resiatancg.
The present invention is to provide, upon conquerinq such defects of the conventional art, an artificial stone molded product which enables the cost to dscrease by the selective formation of light-eini.ttin9 portions and which prQvonts delamination, dropping and abrasion.
With respect to the composition of the artificial stone, in the present invention, it contains an aggregate of an inorganic material and a resin as basic romponents in the substrate (2), the protrusions (3) and also the embedded grooves (4) in Figures 1 and 2. In this instance, the aggregate of the inorganic material includes a wide variety of materials such as a natural stone, a natural mineral, a synthetic inorganicmaterial, a glass, a metal and the like.
And what is important in the present invention is that a luminous or fluorescent material and an aggregate of a transparent inorganic material or an aggregate of a transparent inorganic material having a surface layer coated with a luminous or fluorescent material is contained in at least a part of tho aggregate of the inorganic material in the light-emitting portions constituting the above-mentioned protrusions (3) or the embedded grooves (4).
When the light-emitting portion contains the aggregate of the transparent inorganic material along with the lumtiinous or fluorescent material, it is indispensable that the weight ratio of both materials is between 1:2 and 1:10 and the sum of both materials is between 80 and 95% by weight based on the overall composition of the light-emitting portion.
Further, when the light-emitting portion contains the aggregate of the transparent inorganic material having the surface coated with the luminous or fluorescent material, it is indispensable that the weight ratio of this material is between S and 65% by weight based on the overall composition of the.
light-emitting portion.
The above-mentioned requirements are defined in view of physical properties such as a delamination resistance, a drop resistance, an abrasion resistands and the like, and a luminousness.
As the aggregate of the inorganic material, a combination of the following two types is preferable. That is, one is a fine powder component of an inorganic material having a size of from to 70 mwsh. This is a fine powder component of an appropriate inorganic material selected from minerals such as silica, rocK, chrysolite, feldspar, pyroxene, mica and the like, natural stones such as granite, metamorphite and the lika, porcelain, glasses, metals and the like.
And along with this fine powder component, a finely divided coa-ponent having a size of 100 mesh-under is preferably used. As this finely divided component, various natural or artificial finely divided components are mentioned. For example, powders of calcium carbonate, aluminum hydroxido and silica rock are easily obtainable finely divided components.
Flsrther, as a part of this finely divided coisqnonent, a component such as manganese dioxide, titanium dioxide, zirconium silicate, iron oxide or the like to adjust a color tone, or a component such as antimony trioxide (pentoxide) , a boron compound, a bromine compound or the like to impart a flame ratardance and an incombustibility may be blended.
The above-mentioned fine powder component acts as a main factor of an appearance and physical properties of the resulting artificial stone molded product. The size of the finely divided component is much smaller than the 100 mesh level in comparison to the fine powder component. The finely divided component enters between the individual particles of the fine powder component and is arranged to fill the space between the particles, contributinQ toward providing propertiea such as a hardness and a pliability of the resultting artificial stone. The weight ratio of the fine powder component and the finely divided component is preferably between 0. 5:1 and 5:1, more preferably bQtwoen 1:1 and 4:1. A'hen the artificial stone molded article of the present invention is formed of a cocnbination of the fine powder component and the finely divided corRponent, the structure of the light-emitting portion Can be considered as follows.
<A> When the luminous or fluorescent material and the aggregate of the transparent inorganic material are used as a part of the aggregate of the inorganic material, it is advisable that the component of the transparent inorganic material is usec3.as at least a part of the fine powder component and the luminous or fluorescent tttztsrial is used as at least a part of the finely divided component.
The fine powder cotnponent as the aggregate of the transparent inorganic material refers to a coniponent of an inorganic material having substantially a high light transmission. The transparency thereof includes various degrees.
A natural or synthetic inorganic material having a relatively high light transmission is to be used in the present invention.
Consequently, the fine powder consponent.of the transparent inorganic material may be colored or have a peculiar color.
Quartz, silica rock, a glass and the like are typically mentioned in the present invention as the fine powder component of the transparant inorganic material. However, it is not limited thereto.
And the artificial stone taolded product of the present inventi.on contains, as a part of the finely divided component, a luminous or fluorescent ccnWnent'having a luminescence or a luminousness accompanied by ultraviolet absorption and having a size of 100 mesh-under. Typical axacnplas of such a component e include a strontium aluminate ltani.nescent material, zinc sulfide and the like. These materials are used in, the present invention.
The fine powder component of the inorganic material which plays a roll as an aggregate of an artificial stone haa a size of from 5 to 70 mash as mentioned above, and this is an indispensable requirement in the combination with the finely divided component of the inorganic material. And the above-mentioned luminous or fluorescent component plays the same roll as the finely divided coMponent, and imparts the light function such as the luminousness or the fluorescence to the artificial stone. It is also indispensable that the size of the luminous or fluorescent component is 100 mash-under as in the finely divided component.
With respect to each of the above-mentioned components of the inorganic materials, the mixing ratio is an important requirement along with its size.
That is, in the aomposition of the artificial stone of t:5e present invention, the, relationship of the weight (W1) of the above-mentioned fine powder ccsnponent of the inorganic material, the weight (Ws) of the finely divided component of the inorganic material and the weight (Ws) of the luminous or fluorescent component is preferably as follows.
Wi : (W=+F1,) =0.5:1 to5:1 W2 : W3 = 1:2 to 10:1 With respect to Wi :(Ws + p,) , it is preferably between 1:1 and 4:1. With respect to WZ : W,, it is preferably betwoen 1:1 and 5:1.
And in the fine powder component of the inorganic material, as mentioned,above, it is advisable that the ratio of the fine powder component of the transparent inorganic material therein has preferably the following relationship (0.5 to 1.0)W=.
The above-mAntioned facts aro required to realize physical properties as an artificial stone, such as a strength, a hardness, a density and the like, and a light function such as a luminousness or a fluorescence.
Specifically, the size of each component is selected, as required, depending on a size and a mixing ratio of each component used in combination. Generally, it is preferable that the size of the finely divided component and the luminous or fluorescent component is between 150 and 250 mesh.
The light function of the artificial stone is further described. With respect to the artificial stone of the present invention, the light function of the luminous or fluorescent artificial stone is realized in such a manner that 1) from 30 to 100% by weight of the fine powder component of the inorganic material is a fine powdar of a transparent inorganic material, and 2) a luminous or fluorescp-nt component of 100 zswsh-under is mixed at the above-mantioned specific ratio. And the characteristic feature in this case is that light can be emitted as light having a thickness. It is not that light is emitted in the surface layer alone as in the prior art, but that light is emitted in the overall thickness of an artificial stone. Thus, the product is excellent in the luminousness and the economics in view of the use of an expensive luminous or fluorescent component.
The reason is aa follows. The use of the fine powder componpnt of the transparent inorganic material as a traneparent aggregate permeates light emitted from outside into the inside of the artificial stone to efficiently absorb the light energy in the luminous or fluorescent component, and the lulninous layer having dispersed therein the luminous or fluorescent component formed of the luminescent material or the like is secured as a great thickness including the inside of the artificial stone, so that a high luminosity can be maintained for a long period of time.
In the light emission, the fine powder component of the transparent inorganic material coer-as to have a high luminosity because it is good in a light transmission.
The ratio of the transparent component occupied in the overall fine powder component is, as mentioned above, between 30 and 100$ by weight. Naturally, in some physical properties of an artificial stone, such as a strangth and the like and some external design, a ratio of 100% is preferable from the standpoint of a light function. Of course, this is not critical. However, when it is iess than 3U% by weight, a desired light function is hardly provided.
<B> When the aggregate of the trs.nsparent inorganic material having the surface baked with the luminous or fluorescent material is used as a part of the aggregate of the inorganic material, it can be used such that at least a part of the fine powder component is transparent, and it has the surface baked with the luminous macerial having a luminescence or the like or the fluorescent material having a luminousness accompanied by ultraviolet absorption. That is, a part or the whole of the fine powder component is the aggregate of the transparent inorganic material having the surface coated with the luminous material or the fluorescent material. Appropriate examples of such an aggregate of the inorganic material having the transparent light include a glass, silica rock and the like.
Regarding the fine powder component incorporated in the coraposition, it is advisable that the ratio (weight) of from 10 to 100% is used in the above-mentioned aggregate of the transparent inorganic material having the surface layer coated with the above-mentioned luminous or fluorescent material.
In the aggregate of the transparent inorganic material, ospecially, the baked coating of the fine powder component, a coating having a thickness of from several-iaicrometers to several tens of mierometers, for example, from S to 50 m, preferably from 20 to 40 (.un is applied to the surface of the particle in the transparent fine powder componant. More specifically,.the coating is applied by the baking at a high temperature of from 120 to 1,200 C.
The fluorescent material to be baked can include various fluorescent materials which have a luminescence or which emit light through ultraviolet-light irradiation, such as strontium aluminate, zinc sulfide and the like.
The baking is conducted not by various known methods, but by mixing the aggregate of the transparent inorganic material, for example, the above-mentioned fine powder component with a dispersion or a paste having dispersed therein a fine powder of a luminescent material such as strontium aluminate or the like and drying the mixture.
In the present invention, it is advisable that the fine powder component of the inorganic material has the specific size as noted above. That is, the fine powder component of the inorganic material has a size of from 5 to 70 mssh as mentioned above. When an upper or lower portion is colored dark using the colored and colorless materials, it is considered that the size of fine particles is changed depending on the colored or colorless condition. However, fine particles which are extremely different in the size shall not be used in large amounts because they deteriorate the strength of the product.
Meanwhile, the size of particles of the finely divided cemponent is 100 mesh-under as noted above. The particles of the finely divided component have to be fully incorporated between the particles of the fine powder cornponent. More specifically, the size ia preferably between 150 and 250 mesh.
And what is ing>ortant in the high-density artificial stone of the present invention is that the aggregate components of these inorganic materials are preferably dispersed uniformly in any portions of the product except in special cases.
E~rther, the resin component can be selected from a wide variety of thermosetting materials_ For example, an acrylic resin, a methacrylic resin and an unsaturated polyester resin are mentioned. Of these, the methaerylie resin is preferable in view of a transparency, a hardness, a strength and the like. The ratio of the resin component is proferably less than 15% by weight, further preferably 10% by waight or less basad on the total composition.
This resin component contributes to covering the fine powder component and the finely divided component which are components forming the above-mentti.oned structure to bind the whole body, and functions to impart a resilience or a tensile strength to a product when an artificial stone is completad. Tha ratio of the aggregate of the inorganic material formed of the fine powder component and the finely divided ecxmponent is limited. That is, it has to be 85$ by weight or more, preferably 89% by weight or more. When it exceeds 95$, the product becomes brittle and is hard to use.
When it is less than 85%, the product becomes too soft to give qualities as a stone. Thus, the product is used in the same range as a resin plate.
This means that the component other than the fine powder cornponent and the finely divided component such as a natural stone and the like, namely, the resin component should not be present in the product in an amount exceeding 15.1 by weight.
When the amount of the resin component exceeds 15%, the product is like plastics, and it is only seemingly an artificial stone. Further, when the amount of the resin component is excessively decreased, a product comes to have an appearance close to a natural color, but it becomes brittls and is unsuitable for actual use. From this standpoint, the amount of the resin component is more preferably between 5 and 11% by weight.
In practicing the present invention, the ratios of thoa components are important. Especially important is a ratio of the resin component to the other component. In the present invention, one of the characteristic features is that a high-density product having a dense texture can be providad. The high density here raferred to means that the fine powder component and the finely divided component contained in the artificial stone product are present in a high density. For exwple, this density ia 2.2 g/an' or more which exceeds the range in the conventional artificial s tone .
It is advisable that the outer surface of the product is polished or roughened. In practice, it is preferable that the broken fine powder component is exposed.
The polishing is a practically convenient method for exposing the dense texture condition inherent in the high-density artificial stone having a deep atmosphere in the present invention.
It is, of course, possible that a part of a surface of a product is polished to expose the fine powder cornponent and a difference with another portion in the same surface is used as a pattern.
Further, when an artificial stone is obtained, it is an important problem what a desired color or design is. Granite or marble is one goal because.a product formed of a natural stone is hardly obtained and a color and a glaze thereof aro beautiful.
In the present invention, the transparent component is used as the fine powder component, making it possible to obtain a product having a glaze of granite, marble or the like. This is because a fine powder obtained by pulverizing a quartz-type natural stone is used as the fine powder component.
The fine powder obtained by pulverizing the quartz-type natural stone is colorless and transparent in many cases. In a non-transparent powder, a transparent often remains slightly.
It is also possible to provide a uniform color and a deep, glazed peculiar tone of color by adding an inorganic pigment, an organic pigment such as an azo pigment or a phthalocyanine pigmant, or various dyes.
In the composition of the artificial stone in the present invention, the product can also be colored by using colored particles having the same size as tho fine powder component, an a color component.
In any case, the color reproducibility can be secured quite easily in comparison to the conventional artificial stono, and a product which is axcellent in a dept and a.Qlaze without discoloration can be obtained.
The high-density artificial stone of the present invention having usually excellent color tone characteristics along with a luminescence, a ultraviolet light-emitting property and the like can have any form, examples of the form being a plate, a bar, a cylinder and the like.
The above-mentioned artificial stone molded product of the prasent invention can be produced by, for example, the following process.
<I> Molded product in which protrusions are light-emitting portions:
Fiqure 3 is a flow chart showing a typical process for producing an artificial stone molded product (1) in which protrusions (3) are light-emitting portions.
That is, this Figure 3 shows a process for producing an artificial stone molded prvduct in which protrusions (3) for a figure or a pattern are integrally provided on a flat surface of a substrate (2) , a main composition comprises an aggregate of an inorganic material and a resin, and at least a part of the protrusions (3) are luminous or fluorescent light-emitting portions, which comprises injecting a mixture (6) for resin molding containing a luminous or fluorescent material having a luminescance or a luminousness accompanied by ultraviolet absorption and an aggregate of a transparent inorganic material or an aggregate of a transparent inorganic material having a surface baked with the luminous or fluorescent material as at least a part of the aggregate of the inorganic material into grooves (51) of a mold (5) which correspond to the protrusions (3) of the molded product and which are formed in the inner bottom surface, then injecting a mixture (7) for resin molding containing an aggregate of an inorganic material into the mold (5), preaa-curing the mixture, withdrawing the product from the mold, and further polishing the product or roughening the product using a water jet or the like as required to produce an artificial stone molded product (1) having light-emitting portions in the protrusions (3) alone.
In the curing upon fitting a male mold (8) , the compression is conducted by pressing with a surface pressure of, for examle, from 5 to 100 kgf/ccm2. In this molding, heating is conducted at a temperature of from approximately 90 to 140 C for from 5 to 20 minutes in tha compression.
Tha mixture (6) for resin molding which forms the light-esnitting portions as the protrusions (3) and the mixture (7) for resin molding which forms the substrate (2) are integrally molded in the above-mentioned curing step by the compression.
Accordingly, delamination or dropping of the light-emitting protrusions (3) does not occur. Besides, the protrusions (3) are also formed as having an excellent abrasion resiatance due to its cornposi tion .
This process using such a cotnpression molding exhibits a i6 mass-production effect as a process for produc.ing a product with a relatively simple shape, such as a flat molded product, and there is almost no loss of a material, so that this process is economically excellent too.
A means for surface polishing is not particularly limited.
It can be conducted using a tool such as a grindstone, a polishing cloth, a polishing belt or the like, or a polishing agent such as a buff polishing agent, a rubbing compound or the like.
As the polishing agent, diamond, boron carbide, corundum, alumina and zirconia which have mainly a polishing action, and tripoli, dromite, alumina, chromium oxide and cerium oxide which have mainly a scratching action are used as required.
And in the present invQntion, the surface of the molded product after the molding may be roughened to expose the finely divided couponent to the 'surface portion.
To this end, a method of selectively removing the rosin component is employed. That is, it is effective; for example, that after the product is removed from the mold, high-pressure water is jetted on the surface of the molded product to conduct the texture treatment.
Since this treatment varies dependtng on various conditions such as a thickness, a distance from a nozzle, a treatment mode and the like, it is not limitative. However, usually, in the case of a thickness of from 2 to 20 ean, a water pressure of from 50 to 1,400 kg/czn= can be applied from a height of a noz2lo of froen 2 to 50 cra. This water pres9ura is far lower than when a natural stone is used.
That is, this is because the high-quality treatment can be conducted more easily by the presence of a rosin coanponont.
A nozzle for jetting high-pressure water or its system is not particularly limited. Various types are employable.
The surface is flattened or roughened using the water jet in the texture treatment to produce an artificial stone having a deep quality.
The presence of the resin component does not make the surface cloudy, and makes easy the treatment of a waste wster in comparison to an etching method using chemicals.
Naturally, the surface can be treated with an organic solvent as required to soften or melt the resin component and partially remove the same.
In this case, the organic solvent correaponding to the resin component may be selected. Examples thereof include halogenated hydrocarbons such as methylene chloride and chloroform, carboxylic acids and esters thereof such as acetic anhydride, ethyl acetate and butyl acetate, acetone, tatrahydrofuran, DMF
and DM30.
The molded product is dipped in these orQanic solvents or these organic solvents are sprayed thereon or caused to flow down thereon to remove the resin component softened or melted from the surface whereby the uneven surface can be formed.
Alternatively, the uneven surface may be formed by scratching the resin component having a low hardness from the surface with a wire brush, a cutting means or the like.
The surface is xoughonoddby the above-mentioned various means, and the texture is treated. Then, the resulting surface is polished as noted above to realize the peculiar deep, glazed surface.
<II> Molded product in which embedded grooves are light-emitting portions:
Figure 4 is a flow chart showing a typical process for producing an artificial stone molded product (1) in which embodded grooves (4) are light-emitting portions.
That is, this Figure 4 shows a process for producing an artificial stone molded product in which aenbedded grooves (4) for a figure or a pattern are integrally provided in a flat surface of a substrate (2 ), a main composi tion comprises an aggregate of an inorganic material and a resin, and luminous or fluorescent light-emitting portions are embedded in at least a part of the embedded grooves (4), which comprisas injecting a mixture (7) for resin molding containing an aggregate of an inorganic material into a mold (5) having protrusions (52) corresponding to the meibedr3ed grooves (4) of the molded product in the inner bottom surface, curing or half-curing the mixture, withdrawing the resulting product from the mold, injecting a mixture (6) for resin molding containing a luminous or fluorescent ma.terial having a luminescence or a luminousness accompanied by ultraviolet absorption and an aggregate of a transparent inorganic material or an aggregate of a transparent inorganic material having a surface baked with the luminous or fluorescent material as at ieast a part of the aggregate of the inorganic material into grooves formed in the surface of the molded product to produce an artificial stone molded product (1) having the light-anitting portions in the embedded grooves (4) alone.
In this process as well, the curing by compression molding can be conducted in the above-mentioned manner, and the surface of the molded product (1) ie likewise finally polished or roughened as required. The mixtures (6) ,(7) for resin molding are also integrated.
For example, when the aggregate of the transparent inorganic material having the surface coated with the luminous or fluorescent material is used as the mixture (6) for resin molding in either process, the soctions of the particles and the coating layer are exposed by treatment such'as polishing or the like.
In this manner also, an artificial stone which is excellent in light-emitting characteristics, a texture and qualities is produced.
That is, for example, when a luminescent or ultraviolet light-emitting material is baked and coated on the surface of the fine powder component, the particles of the fine powder component and the coating thereof are exposed as sections by polishing the surface of the artificial stone. Consequently, light irradiated from outside is entered frosn the exposed particle surface of thA
transparent fine powder and reaches the baked coating material in the inside.
In the case of a highly transparent methacrylic resin or the like, the light transmission is rendered wholly good.
For this reason, incident light ss transmitted into the inside of the light-emitting portion, and light is also emitted from inside.
Accordingly, light can be stored in a short period of time, and a light-emitting efficiency is also increased.
The present invention is illustrated by referring to the following Examples. Naturally, the present invention is not limited to the following Exaunples.
EXAMPLE
Example 1 An artificial stone molded product was produced according to a process shown in Figure 3.
That is, a mixture (6) for resin mOlding having the following fozinulation was injected into grooves (51) having a depth of 6 rrm in a mold (5).
Silica rock of from 10 to 50 mesh in which 60% by weight a surface layer baked with a strontium aluminate luminescent material at approximately 11000 C was formed to a thickness of approximately 30 pm Silica rock powder having an average 30% by weight particle diameter of 250 mesh Methyl methacrylate (MM) (containing 10% by weight 0.15$ of a peroxide-type curing agent) Subsequently, a mixture (7) for resin molding having tha following formulation was injected into the mold (5).
Silica rock of from 10 to 70 mesh 20-t by weight Silica rock of from 10 to 70 mesh having 42% by weight on tho surface a baked layer of a yellow pigment with a thickness of 30 rn Aluminum oxide powder having an average 30$ by weight particle diameter of 225 mesh Methyl mathacrylate (Hmk) (containing 8$ by weight 0.15% of a peroxide-type curing agent) An upper mold (8) was placed theroon, and the mixture was pressed and cured at a temperature of 120 C and a prQSsure of 12 kgf/an2 for 20 minutes.
Then, the product was withdrawn from the mold to obtain an artificial atone molded product (1) in which the thickness of the substrate (2) was 20 nsn and the height of each of the protrusions (3) was 6 mm.
With respect to this molded product (1) , the surface of t.he protrusion (3) was adjusted to a height of 5 nan by polishing the same with a diamond grindstone.
In the resulting molded product (1), the protrusion (3) polished had a light-emitting property such as a luminousness, and exhibited an excellent performance as a position guide mark in dark surroundings. Further, the substrate (2) had an excellent decorativeness as a deep yellow plate, was beautiful even in the daytime and could be used also as a braille block for a blind peraon.
In a test according to JIS K-7112, the apecific gravity was 2.30. Further, the water absorption was 0.14$. With respect to the properties in the protrusions (3) in a region where the substrate (2) and the protrusions (3) were inteqrated, the hardness, the abrasion resistance and the like were excellent as shown in Table 1.
Table 1 item Results Test conditions Sending 63.55 kgf cm aaaordinQ to JI8 A-5209 strength Compression 1380 kgf/cn Crosshead speed 0.5 mm/min strength Load call 2 tons Impact 4,57 kgf=cm/am2 Pendulum impact test strength Hardness 1020 kgf/mn Vickers hardness according to Abrasion 0.01 g J2S A-5209 sand dropping-type rasistance abrasion test Further, no abnormality was observed even in tests for an acid resistance and an alkali resistance by the dipping in a 3*
hydrochloric acid aqueous solution for 8 hours and the dipping in a 3-t sodium hydroxide aqueous solution for 8 hours.
Example 2 The molding was conducted in the same manner as in Example 1, using a mixture (6) for resin molding having the following formulation.
Silica rock of from 10 to 50 mesh in which 50% by weight a surface layer bakod with a strontium aluminate luminescent material at approximately 1,000 C was formed to a thickness of approximately 30 (,tm Silica rock powder having an average 20% by weight particle diameter of 250 mesh Powder of a strontium alesninate 20% by weight luminescent material=having an average particle diameter of 220 mesh Methyl mathacrylate (KIA) (containing 10% by weight 0.2$ by weight of a peroxide-type curing agent) . Th protrusions (3) were polished using a diamond grindstone and a silicon carbide magnosia grindstone. Further, the resin portion alone in the surface portion was removed at a water jet pressure of 1, 200 kg/cm2 (nozzle diameter 0. 8 mm, a jat distance 35 men).
The resulting artificial stone had a depth and a non-slip property in the daytime, and could be seen in the overall thickness direction at night for a long period of time because of the luminescence.
It could be used as a lumi.nous guide mark building material in urgent power failure and thus as an effective artificial stone.
Example 3 The molding was conducted in the same manner as in Example 1, using a mixture (6) for resin molding having the following formulation.
Silica rock of from 10 to 60 mesh 60* by weight Aluminum hydroxide powder having an 22'b by weight average particle diameter of 220 mesh Strontium aluminate luminescent 10-t by weight material havinq an average particle diameter of 200 mesh M~thyl methacrylate (A!MM (containing 8% by weight 0.15'b of a peroxide-type curing agent) Likewise, a molded product which was excellent in physical properties and a luminousness waa obtained.
Example 4 An artificial stone molded product having a thickness of 16 nsn in which embedded, grooves (4) having a depth of 4 rRn were light-em.itting portions was obtained by the process in Figure 4, using the mixtures (6), (7) for resin molding in Exairrple 1.
The surface was polished by means of a diamond grindstone.
A molded product which was excellent in physical properties and a luminousness was obtained.
INDUSTRIAL APPLICABILITY
As stated above, the present invention provides a high-density artificial stone which was excella.nt in light properties such as a luminousness and the like, which had a deep, glazed, excellent tone of color, which was free from problems such as delamination, dropping, abrasion and the like of light-emitting portions and which had good physical properties. Sesides, the production of such an excellAnt product is.realized at far lower costs than the ordinary product.
Claims (14)
1. An artificial stone molded product in which protrusions or embedded grooves for a figure or a pattern are provided integrally on or in a flat surface of a substrate, and a main composition comprises an aggregate of an inorganic material and a resin, characterized in that at least a part of said protrusions or embedded grooves are luminous or fluorescent light-emitting portions which contain a luminous or fluorescent material having a luminescence or a luminousness accompanied by ultraviolet absorption and an aggregate of a transparent inorganic material, or an aggregate of a transparent inorganic material having a surface baked with said luminous or fluorescent material as at least a part of the aggregate of the inorganic material.
2. The artificial stone molded product of claim 1, wherein the luminous or fluorescent material is a luminescent material.
3. The artificial stone molded product of claim 1, wherein the luminous or fluorescent material and the aggregate of the transparent inorganic material are contained in the light-emitting portions such that a weight ratio of both of them is from 1:2 to 1:10 and the total amount of both of them is between 80 and 95% by weight based on the total amount of the composition of the light-emitting portions.
4. The artificial stone molded product of claim 1, wherein the aggregate of the transparent inorganic material baked with the luminous or fluorescent material is contained in the light-emitting portions at a ratio of from 5 to 65% by weight based on the total amount of the composition of the light-emitting portions.
5. The artificial stone molded product of claim 1, wherein the aggregate of the transparent inorganic material is a glass, quarts or silica rock.
6. The artificial stone molded product of claim 1, wherein the resin is a methacrylic resin.
7. The artificial stone molded product of claim 1, wherein the ratio of the aggregate of the inorganic material is between 89 and 95% by weight based on the weight of the molded product, and tho ratio of the resin is between 5 and 11% by weight based on the weight of the molded product.
8. The artificial stone molded product of claim 1, wherein the aggregate of the inorganic material comprises a fine powder component having a size of from 5 to 70 mesh, and a finely divided component having a size of 100 mesh-under.
9. The artificial stone molded product of claim 8, wherein in the light-emitting portions, at least a part of the fine powder component contained is a fine powder component of a transparent inorganic material, and at least a part of the finely divided component is a luminous or fluorescent material.
10. The artificial stone molded product of claim 8, wherein in the light-emitting portions, at least a part of the fine powder component contained is a transparent inorganic material having a surface baked with a luminous or fluorescent material.
11. The artificial stone molded product of claim 8, wherein the weight ratio of the fine powder component to the finely divided component is between 1:1 and 4:1.
12. The artificial stone molded product of claim 10, wherein the thickness of the coating layer of the luminous or fluorescent material is between 5 and 50 µm.
13. A process for producing an artificial stone molded product in which protrusions for a figure or a pattern are integrally provided on a flat surface of a substrate, a main composition comprises an aggregate of an inorganic material and a resin, and at least a part of the protrusions are luminous or fluorescent light-emitting portions, so that the light-emitting portions are present only in said protrusions, which comprises injecting a mixture for resin molding containing a luminous or fluorescent material having a luminescence or a luminousness accompanied by ultraviolet absorption and an aggregate of a transparent inorganic material or an aggregate of a transparent inorganic material having a surface baked with said luminous or fluorescent material as at least a part of the aggregate of the inorganic material into grooves of a mold which correspond to the protrusions of the molded product and which are formed in the inner bottom surface, than injecting a mixture for resin molding containing an aggregate of an inorganic material into the mold, curing the mixture, and withdrawing the product from the mold.
14. A process for producing an artificial stone molded product in which embedded grooves for a figure or a pattern are integrally provided in a flat surface of a substrate, a main composition comprises an aggregate of an inorganic material and a resin, and luminous or fluorescent light-emitting portions are embedded in at least a part or said embedded grooves, so that the light-emitting portions are present only in said embedded grooves, which comprises injecting a mixture for resin molding containing an aggregate of an inorganic material into a mold having protrusions corresponding to the embedded grooves of the molded product in the inner bottom surface, curing or half-curing the mixture, withdrawing the product from the mold, injecting a mixture for resin molding containing a luminous or fluorescent material having a luminescence or a luminousness accompanied by ultraviolet absorption and an aggregate of a transparent inorganic material or an aggregate of a transparent inorganic material having a surface baked with the luminous or fluorescent material as at least a part of the aggregate of the inorganic material into grooves formed in the surface of the molded product, and curing the mixture.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002253807A CA2253807A1 (en) | 1997-03-05 | 1997-03-05 | Artificial stone molded product |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002253807A Division CA2253807A1 (en) | 1997-03-05 | 1997-03-05 | Artificial stone molded product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2590599A1 CA2590599A1 (en) | 1998-09-11 |
| CA2590599C true CA2590599C (en) | 2009-08-25 |
Family
ID=38606814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002590599A Expired - Fee Related CA2590599C (en) | 1997-03-05 | 1997-03-05 | Artificial stone molded product |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2590599C (en) |
-
1997
- 1997-03-05 CA CA002590599A patent/CA2590599C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2590599A1 (en) | 1998-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6136226A (en) | Noctilucent or fluorescent artificial stone composition | |
| AU746444B2 (en) | Artificial stone | |
| EP0983977B1 (en) | Artificial stone | |
| CN100453616C (en) | Luminous and luminescent artificial stone and its structure | |
| US6627315B2 (en) | Artificial stone | |
| JP4046149B2 (en) | Luminous or fluorescent artificial stone | |
| US6500543B2 (en) | Artificial stone molded product | |
| EP0906894B1 (en) | Formed artificial stone | |
| JPH11292595A (en) | Artificial stone luminescent molded body | |
| JP4067170B2 (en) | Artificial stone molding | |
| CA2590599C (en) | Artificial stone molded product | |
| EP1693354A2 (en) | Artifical stone molded product | |
| AU779665B2 (en) | Formed artificial stone | |
| JP4126669B2 (en) | Artificial stone molding | |
| AU779786B2 (en) | Noctilucent or fluorescent artificial stone composition | |
| CA2257425C (en) | Artificial stone | |
| KR100605234B1 (en) | Internal and external snow | |
| WO1998057316A1 (en) | Internal and external building material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20170306 |