CN1673164A - Method for producing artificial stone - Google Patents
Method for producing artificial stone Download PDFInfo
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- CN1673164A CN1673164A CN 200410058921 CN200410058921A CN1673164A CN 1673164 A CN1673164 A CN 1673164A CN 200410058921 CN200410058921 CN 200410058921 CN 200410058921 A CN200410058921 A CN 200410058921A CN 1673164 A CN1673164 A CN 1673164A
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Abstract
This invention provides a manufacturing method of an artificial stone which has a light weight and compression and bending strength, and shows depth such as marble or onyx. The manufacturing method comprises a process of applying an unsaturated polyester resin for gel coating on the inner side bottom surface 13 and the inner side vertical surface 14 of a mold frame 12, a process of curing the unsaturated polyester resin for gel coating, thereafter compounding an unsaturated polyester resin, a low profile additive, a fine inorganic filler, a curing agent and a coloring pigment, each amount being predetermined, and pouring the base compound of the mixed and degassed resin material in the mold frame 12 to form an underlayer 18 having predetermined thickness, a process of placing a laminated plywood 19 insertable in the mold frame 12 keeping a clearance and having thickness corresponding to the thickness of the article on the underlayer 18, a process of casting the resin material in the surrounding of and on the laminated plywood 19 up to the upper surface of the mold frame 12, and a process of curing it and removing the molded article 15 from the mold frame 12.
Description
Technical field
The present invention relates to a kind of preparing artificial stone of using unsaturated polyester resin.
Background technology
In the past, as the artificial stone-like material of stone materials such as imitation marble etc., the terrazzo that known useful white cement solidifies the marble grain and its surface is ground, and the stone grain of marble or flower web plate etc. sneaked into the artificial stone-like material who obtains after solidifying in the resin.Again, patent documentation 1 (No. 2551858 communique of Japanese Patent) discloses a kind of like this manufacture method for artificial marble, and described manufacture method for artificial marble comprises: the 1st operation that in the bottom is the inboard release agent application of plane glass seat molding box; Apply transparent resin on the glass seat in molding box, under the half-dried state of described transparent resin, place stencil paper, the limit deflates, and the limit makes transparent resin and stencil paper connect airtight adherent the 2nd operation; The 3rd operation of the back lining materials of the mixture of coating stone grain and resin on stencil paper; On described back lining materials, put into wooden core material, reach the 4th operation that is covered with described back lining materials more thereon on every side; And after placing appropriate time, the 5th operation that the artificial marble that forms is unloaded from molding box.
Yet, have than great, Heavy Weight, the bothersome problem of construction with artificial stone-like material method manufacturing in the past, that in all, contain the stone grain.Though also existing, described artificial stone-like material has excellent compressive strength, the problem of anti-folding strength difference again.
Secondly, the artificial marble of patent documentation 1 described invention, owing to wherein add wooden core material, therefore can make light specific gravity, have the excellent compression and the artificial marble of anti-folding strength, but the occasion that rounding is handled is carried out at the angle of this artificial marble at need, expose if grind or cut then the end of stencil paper, so make processing difficulties.In addition, the problem that above-mentioned marble exists also has, and can only form the same pattern that is formed by stencil paper, and compared with natural marble or onyx stone (onyx marble), its pattern depth is little,, lacks stereoscopic sensation that is, is complanation.
Summary of the invention
The present invention system does in view of the above problems, the object of the present invention is to provide a kind of preparing artificial stone, described artificial stone-like material is in light weight and have excellent withstand voltage, anti-flexural strength, has depth of pattern as natural marble or onyx stone (onyx marble).
According to described purpose, technical solution of the present invention 1 described preparing artificial stone comprises the operation of following (1)～(5).
(1) pre-prepd, by having on the molded platform that certain thickness float glass or stainless steel plateform constitute, the operation of coated surfaces unsaturated polyester resin for coating on the inside bottom surface of the molding box that forms by the wall material framework that uses float glass or hard resin material and inboard vertical surface;
(2) after above-mentioned top coat solidifies with unsaturated polyester resin, to put into described molding box by the refining sizing material (basecompound) of joining that resin material is formed, form the operation of the stratum basale of specific thickness, described resin material is the unsaturated polyester resin of relative 100 weight parts, allocate micro mist 200～400 weight parts, solidifying agent 0.4～3.5 weight part and the appropriate colouring pigment of shrinking agent 10～40 weight parts, inanimate matter stopping composition into, stir and deaeration is handled and got;
(3) also can leave and pack into gap in the above-mentioned molding box and be stated from operation on the above-mentioned stratum basale with the veneer sheet of products thickness respective thickness;
(4) on reach around the above-mentioned veneer sheet, pour into a mould the operation of above-mentioned resin material until the molding box upper surface;
(5) after above-mentioned resin material solidifies at normal temperatures,, obtain proportion and be 1.0～1.1 light weight, be difficult for the operation of rimose moulded product from the described molding box demoulding.
According to above-mentioned purpose, technical solution of the present invention 2 described preparing artificial stone comprise the operation of following (1)～(5).
(1) pre-prepd, by having on the molded platform that certain thickness float glass or stainless steel plateform constitute, the operation of coated surfaces unsaturated polyester resin for coating on the inside bottom surface of the molding box that forms by the wall material framework that uses float glass or hard resin material and inboard vertical surface;
(2) after above-mentioned top coat solidifies with unsaturated polyester resin, to join the refining sizing material and put into described molding box, form the operation of the stratum basale of specific thickness, the described refining sizing material of joining is with (a) relative unsaturated polyester resin 100 weight parts, allocate shrinking agent 10～40 weight parts into, micro mist 200～400 weight parts of inanimate matter stopping composition, solidifying agent 0.4～3.5 weight part and appropriate colouring pigment, stir and deaeration is handled and the resin material that obtains, (b) relative unsaturated polyester resin 100 weight parts, allocate shrinking agent 10～40 weight parts into, micro mist 200～400 weight parts of inanimate matter stopping composition, solidifying agent 0.4～3.5 weight part and an amount of and tinting pigment above-mentioned tinting pigment different colours, stir and deaeration is handled and the decorative pattern that obtains appears material, be mixed to the degree that color do not merge and form;
(3) can leave again and pack into gap in the above-mentioned molding box and be stated from operation on the above-mentioned stratum basale with the veneer sheet of products thickness respective thickness;
(4) on reach around the above-mentioned veneer sheet, pour into a mould above-mentioned resin material or above-mentioned operation of joining the refining sizing material until the molding box upper surface;
(5) after above-mentioned resin material solidifies at normal temperatures,, obtain proportion and be 1.0～1.1 light weight, be difficult for the operation of rimose moulded product from the described molding box demoulding.
According to above-mentioned purpose, technical solution of the present invention 3 described preparing artificial stone comprise the operation of following (1)～(5).
(1) pre-prepd, by having on the molded platform that certain thickness float glass or stainless steel plateform constitute, the operation of coated surfaces unsaturated polyester resin for coating on the inside bottom surface of the molding box that forms by the wall material framework that uses float glass or hard resin material and inboard vertical surface;
(2) after above-mentioned top coat solidifies with unsaturated polyester resin, with (a) relative unsaturated polyester resin 100 weight parts, allocate shrinking agent 10～40 weight parts into, micro mist 200～400 weight parts of inanimate matter stopping composition, solidifying agent 0.4～3.5 weight part and appropriate colouring pigment, stir and deaeration is handled and the resin material that obtains, (b) relative unsaturated polyester resin 100 weight parts, allocate shrinking agent 10～40 weight parts into, micro mist 200～400 weight parts of inanimate matter stopping composition, solidifying agent 0.4～3.5 weight part and an amount of and tinting pigment above-mentioned tinting pigment different colours, stir and deaeration is handled and the decorative pattern that obtains appears material, seamlessly pack in the molding box, play the operation that specific thickness forms stratum basale from the inside bottom surface of above-mentioned molding box;
(3) have again, can leave in the above-mentioned molding box of packing into gap and have veneer sheet with the products thickness respective thickness and be stated from operation on the above-mentioned stratum basale;
(4) on reach around the above-mentioned veneer sheet, pour into a mould above-mentioned resin material or decorative pattern and appear the operation of material until the molding box upper surface;
(5) after above-mentioned resin material solidifies at normal temperatures,, obtain proportion and be 1.0～1.1 light weight, be difficult for the operation of rimose moulded product from the described molding box demoulding.
In technique scheme 1～3 described preparing artificial stone, molded is for example float glass about 8～10mm or the plate shaped one-tenth of stainless steel by having thickness, molding box is on molded platform, thickness is that the float glass of 2.5～6mm (for example about 3mm) or the wall material framework of hard resin material (for example, polyvinyl chloride or polyvinyl resin etc.) form by for example using.Molding box can form to overlook and be trilateral, Polygons, circle, ellipse and other arbitrary shapes a kind of more than the tetragon, also can form the combined shaped of these shapes.
Use the wall material of hard resin material, for example, be included in the occasion of the inside sidewalls applying hard resin material that forms by thin glued board etc.Again, top coat can use the resin of transparent (can have an X-rayed the color of degree but also how much have some its inside) with unsaturated polyester resin, and its thickness is applied to about 0.5mm (also 0.3～1mm).In addition, be preferably, release agent application on the inside bottom surface of molding box and inboard vertical surface in advance is so that the demoulding.
Relative unsaturated polyester resin 100 weight parts, allocate micro mist 200～400 weight parts, solidifying agent 0.4～3.5 weight part and the appropriate colouring pigment of shrinking agent 10～40 weight parts, inanimate matter stopping composition into, for example the limit is stirred, is mixed with stirrer, the limit carries out being handled by for example vacuum defoamation, makes to have the mobile resin material of appropriateness.Utilize the carrying out of deaeration, can prevent from resin material, to form pin hole shape hole.
Unsaturated polyester resin is added solidifying agent carry out thorough mixing, then produce polyreaction in unsaturated polyester resin, unsaturated polyester resin solidifies gradually, becomes solid state.By the inanimate matter packing material micro mist and the coloured material that cooperate, can manual shift obtain the color and the texture of various stone materials.Again,, be preferably,, make it to solidify, thus, can make arbitrary shape, and artificial stone-like material's (moulded product) of size with the curing catalyst mixed together with unsaturated polyester resin and solidifying agent.
As unsaturated polyester resin, can make 1) be selected from unsaturated dibasic acid (comprising its acid anhydrides) as one or two or more kinds of toxilic acid, toxilic acid liver, fumaric acid, methylene-succinic acid, citraconic acid, chloromaleic acid, equisetic acid and dihydro muconic acid, with 2) be selected from as ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol, T glycol, neopentyl glycol, 1,3-butyleneglycol, 1, the polycondensate of the polyvalent alcohol of one or two or more kinds of 6-hexylene glycol and hydrogenation dihydroxyphenyl propane, 3) add again and make as the linking agent of a kind of of vinyl monomer and styrene monomer or two kinds of compositions.
Again, unsaturated polyester resin is preferably and uses viscosity to be for example 250～500mPas (pascal second).Less than 250mPas, then viscosity is low as the viscosity of unsaturated polyester resin, and is puckery refreshing, is difficult to use; And if the viscosity of unsaturated polyester resin surpasses 500mPas, and is then really up to the mark, and import bubble easily.Because unsaturated polyester resin is a light transmission, therefore, can have an X-rayed and see internal structure, obtains having the artificial stone-like material of depth sense.
Shrinking agent is used to reduce and solidifies the contraction that volumetric shrinkage is about 6～10% unsaturated polyester resin, reduces the warpage (concavo-convex) of moulded product and reverses.As shrinking agent, the shrinking agent that can use general unsaturated polyester resin to use.Unsaturated polyester resin 100 weight parts are allocated 10～40 weight parts into relatively, are preferably, and allocate 20～30 weight parts into.The warpage of moulded product as less than 10 weight parts, then takes place and reverses in the use level of shrinking agent relative unsaturated polyester resin 100 weight parts easily; Surpass 40 weight parts, then react passivation, the solidified of being difficult to possibility is arranged.
As shrinking agent, can enumerate: 1) lower alkyl esters of acrylic or methacrylic acid (for example, be selected from one or more of methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methyl acrylate and ethyl propenoate), 2) any independent polymkeric substance or its two or more copolymer analog of vinylbenzene, vinylchlorid and vinyl acetate.Have again, as above-mentioned shrinking agent, also can be at least a in the above-mentioned vinyl monomer and contain lauryl methacrylate(LMA), the different vinyl acetate of methacrylic acid, acrylamide, Methacrylamide, vinylformic acid hydroxyalkyl acrylate or methacrylic ester, vinyl cyanide, methacrylonitrile, vinylformic acid, methacrylic acid, and any monomeric at least a multipolymer of methacrylic acid cetearyl alcohol acid esters.As above-mentioned shrinking agent, for example, form by any of rhodia (ester), cellulose acetate propionate, polyethylene, polypropylene and saturated polyester again.
Contraction when inanimate matter packing material micro mist is used to relax unsaturated polyester resin curing and raising artificial stone-like material's texture.As the inanimate matter packing material, for example can use, aluminium hydroxide, lime carbonate, talcum, and moisture stone flour one or two or more kinds, particle diameter is the fine-powder of 50～100 μ m.The inanimate matter packing material can add in the scope that relative unsaturated polyester resin 100 weight parts are 200～400 weight parts.As the addition of relative unsaturated polyester resin 100 weight parts of inanimate matter packing material less than 200 weight parts, contraction alleviation effects when then unsaturated polyester resin solidifies is not good, addition as relative unsaturated polyester resin 100 weight parts of inanimate matter packing material surpasses 400 weight parts, and then artificial stone-like material's intensity is low.
As solidifying agent, by cross ester class, and any solidifying agent of forming of peroxocarbonate class by commercially available diallyl peroxide, peroxyesters, hydroperoxide kind, dialkyl peroxide class, ketone peroxide class, superoxide ketals, alkyl, for example, can use methylethyl ketone peroxide as 55% concentration of ketone peroxide class (organo-peroxide class).In addition,,, be preferably for promote solidifying in the occasion of low-temperature curing unsaturated polyester resin, and with the metal bases, tertiary amines, the quaternary amine that are selected from cobalt system, vanadium system or manganese system etc., reach the curing catalyst of at least a composition of thio-alcohol.For example, can use the naphthoic acid cobalt of 1% concentration.
The use level of solidifying agent can be relative unsaturated polyester resin 100 weight parts, allocates solidifying agent 0.4～3.5 weight part into, is preferably 0.5～3.0 weight part.As the amount of allocating into of relative unsaturated polyester resin 100 weight parts of solidifying agent less than 0.4 weight part, then be difficult to solidify, and its amount of allocating into surpasses 3.5 weight parts, though rapid gelatinizing then takes place sometimes, but still can take place sometimes uncured, unsaturated polyester resin generation variable color.Again, when using curing catalyst, unsaturated polyester resin 100 weight parts can be allocated curing catalyst 0.4～1.3 weight part into relatively, are preferably 0.4～1.0 weight part.As the amount of allocating into of relative unsaturated polyester resin 100 weight parts of curing catalyst less than 0.4 weight part, then solidify the end and obtain promoting, and its amount of allocating into surpasses 1.3 weight parts, though rapid gelatinizing then takes place, but uncured phenomenon takes place sometimes, unsaturated polyester resin generation variable color.By the interpolation of curing catalyst, can be in summer and winter whole, guarantee duration of service, unsaturated polyester resin is solidified.
As tinting pigment, can use commercially available polyester pigment, can give the artificial stone-like material by this with shades of colour.Tinting pigment can be an amount of, but be preferably, and the amount of allocating into of unsaturated polyester resin 100 weight parts is the scope of 0.04～5.0 weight part relatively.
In the preparing artificial stone of technical scheme 2 and 3, appear material as decorative pattern, can use the tinting pigment that is different from above-mentioned resin material to make.Again, be used for the unsaturated polyester resin that decorative pattern appears material, its concentration preferably is higher than the viscosity of the unsaturated polyester resin that is used in resin material, appears the color of material and the blend of colors of resin material not make decorative pattern.Appear the use of material by decorative pattern, the artificial stone-like material with multicolour, obtain to have more relief onyx stone (onyx marble) decorative pattern.Again,, make the veneer sheet vibration, make decorative pattern appear material and resin material natural fusion, reveal the degree of depth by for example vibrator carrying when holding veneer sheet.
Again, in technical scheme 2 described preparing artificial stone, so-called " being mixed to the degree that color does not merge " is meant, is mixed to the degree that the unlikely mixing of color becomes other colors.
In technical scheme 1～3 described preparing artificial stone, make in the operation of resin material, making decorative pattern in addition in technical scheme 2,3 described preparing artificial stone appears in the manufacturing process of material, also can in stirring unsaturated polyester resin, shrinking agent, inanimate matter packing material powder, solidifying agent and coloured material, allocate defoamer into, thus, can when stirring above-mentioned materials, remove the air of bringing into effectively at short notice.Defoamer can use commercially available polyester defoamer.
Again, the thickness of stratum basale is preferably and is formed on 6～15mm.Less than 6mm, then can see veneer sheet wherein as the thickness of stratum basale, perhaps, warpage can take place or reverse.In addition, greater than 15mm, then the usage quantity of resin material increases as the thickness of stratum basale, cost up, and simultaneously, shorten the set time of stratum basale, and thermal value increases, and warpage or cracking etc. take place easily, causes artificial stone-like material's quality to descend.
Have, be preferably, the veneer sheet on the stratum basale uses glued board, and making can certain interval (makes between the face of the molding box medial surface veneer sheet corresponding with it and is divided into, for example, 8～15mm) sizes of packing in the molding box, its thickness makes the numerical value that deducts 12～30mm from finished product thickness.In addition, in the thin occasion of finished product thickness, also the thickness of the veneer sheet of packing into can be made finished product thickness pact half.
By the use of veneer sheet, can be in contraction that alleviates the artificial stone-like material and warpage, gain in strength in, weight reduction.And, the artificial stone-like material being used for occasions such as desk, wood screw directly can be screwed together on the artificial stone-like material, and need not bearer.
Be preferably, hammer be stated from make its weight pressing stratum basale and veneer sheet on the veneer sheet.As hold under the state of hammer carrying, normal temperature (for example, 15～30 degree), placed 20～60 minutes, make the unsaturated polyester resin polymerization, stratum basale curing simultaneously, makes stratum basale and veneer sheet bonding.Have, above reaching around veneer sheet,, for example carry out after the molding box upper surface at the casting resin material again, the curing about 4～15 hours, under the normal temperature from the molding box demoulding, obtains moulded product.
In technical scheme 1～3 described preparing artificial stone, around the resin material that forms stratum basale and the input horizon pressing plate and on the composition of resin material can be identical, its composition is so long as the scope in main points of the present invention, even change also applicable the present invention to some extent.Join the refining sizing material and technical scheme 3 described decorative patterns appear in the material in that technical scheme 2 is described again, inject around stratum basale and the veneer sheet and on the composition of resin material so long as the scope in main points of the present invention also is suitable for the present invention even change to some extent.
Technical scheme 4 described preparing artificial stone tie up in the technical scheme 3 described preparing artificial stone, and according to the operation of above-mentioned formation stratum basale, above-mentioned decorative pattern appears material and pours into a mould with cast utensil (that is, injecting container).In technical scheme 4 described preparing artificial stone, as the cast container, have, for example, store decorative pattern and appear container of material and be arranged at nozzle on the container, have the utensil that appears material as discharge decorative patterns such as the cylinder in the form of piston as the syringe, pumps.By the decorative pattern of instrument used for injection appear the relief outlet of material bore, and decorative pattern appear the variation of the pouring speed (velocity of discharge) etc. of material, can obtain diversified decorative pattern.Also can use the cast of cast utensil to join refining sizing material and resin material again.
Technical scheme 5 described preparing artificial stone tie up in technical scheme 2～4 described preparing artificial stone, according to the operation of above-mentioned formation stratum basale, mix above-mentioned resin material and above-mentioned decorative pattern appears material, and its border color is not merged.In technical scheme 5 described preparing artificial stone, the stirring of color boundaries can be carried out with utensils such as for example round end scrapers, thus, can form gyrate decorative pattern on the artificial stone-like material.
Technical scheme 6 described preparing artificial stone tie up in technical scheme 2～5 described preparing artificial stone, have multiple above-mentioned decorative pattern and appear material, and use different tinting pigments attached with color respectively.
Technical scheme 7 described preparing artificial stone tie up in technical scheme 1～6 described preparing artificial stone, with process furnace above-mentioned moulded product are imposed regelate and handle.In technical scheme 7 described preparing artificial stone, regelate is for example, 30～50 ℃ of temperature, is preferably 40～50 ℃, heat treated 3～4 hours.Process furnace can use ventilated type.Regelate be preferably the atmosphere temperature in workshop 30 ℃ less than condition under carry out, the atmosphere temperature in workshop particularly in summer, can be omitted regelate 30～40 ℃ occasion.In the regelate operation, its Heating temperature is as less than 30 ℃, and then moulded product can not completely solidified, above 50 ℃, then veneer sheet is different with the thermal expansivity of the resin material with unsaturated polyester resin and inanimate matter packing material, the generation that causes warpage or reverse.
Technical scheme 8 described preparing artificial stone tie up in the manufacture method of technical scheme 1～7 described material, and described moulded product is processed to described veneer sheet is left certain thickness, again at its surface applied top coat unsaturated polyester resin.In technical scheme 8 described preparing artificial stone, residual thickness, promptly the thickness around the veneer sheet is preferably, and for example makes 6～15mm.Less than 6mm, then can see veneer sheet wherein as above-mentioned thickness, warpage perhaps take place, reverse.
Technical solution of the present invention 1 and subordinate technical scheme 7 thereof and 8 described preparing artificial stone comprise: (1) operation of coated surfaces unsaturated polyester resin for coating on the inside bottom surface of molding box and inboard vertical surface, (2) after above-mentioned top coat solidifies with unsaturated polyester resin, to put into described molding box by the refining sizing material of joining that resin material is formed, formation has the operation of certain thickness stratum basale from the inside bottom surface of molding box, (3) again veneer sheet is stated from operation on the above-mentioned stratum basale, (4) on reach around the above-mentioned veneer sheet, pour into a mould the operation of above-mentioned resin material until the molding box upper surface
(5) after above-mentioned resin material solidifies at normal temperatures,, obtain proportion and be 1.0～1.1 light weight, be difficult for the operation of rimose moulded product from the described molding box demoulding.Thus, can obtain in light weight, have excellent compression, anti-flexural strength, have monochromatic artificial stone-like material as the degree of depth of natural marble or onyx marble (onyx stone).
Technical solution of the present invention 2 and subordinate technical scheme 5～8 described preparing artificial stone thereof comprise: (1) operation of coated surfaces unsaturated polyester resin for coating on the inside bottom surface of molding box and inboard vertical surface, (2) after above-mentioned top coat solidifies with unsaturated polyester resin, resin material and decorative pattern are appeared the degree that material mixing to color does not merge, blended is joined the refining sizing material put into described molding box, formation has the operation of certain thickness stratum basale from the inside bottom surface of molding box, (3) again veneer sheet is stated from operation on the above-mentioned stratum basale, (4) on reach around the above-mentioned veneer sheet, pour into a mould above-mentioned operation of joining the refining sizing material until the molding box upper surface, (5) after above-mentioned resin material solidifies at normal temperatures, from the described molding box demoulding, obtain proportion and be 1.0～1.1 light weight, the operation that is difficult for the rimose moulded product.Thus, can obtain in light weight, have excellent compression, anti-flexural strength, have as natural marble or the natural figure of onyx marble (onyx stone) and the polychrome artificial stone-like material of the degree of depth.
Technical solution of the present invention 3 and subordinate technical scheme 4～8 described preparing artificial stone thereof comprise: (1) operation of coated surfaces unsaturated polyester resin for coating on the inside bottom surface of molding box and inboard vertical surface, (2) after above-mentioned top coat solidifies with unsaturated polyester resin, resin material and decorative pattern are appeared material seamlessly put into molding box, make it to form the operation that reaches certain thickness stratum basale from the inside bottom surface of above-mentioned molding box, (3) veneer sheet is stated from operation on the above-mentioned stratum basale, (4) on reach around the above-mentioned veneer sheet, casting resin material or decorative pattern appear the operation of material until the molding box upper surface, (5) after above-mentioned resin material solidifies at normal temperatures, from the described molding box demoulding, obtain proportion and be 1.0～1.1 light weight, the operation that is difficult for the rimose moulded product.Thus, can obtain in light weight, have excellent compression, anti-flexural strength, can freely be processed into and have as the natural figure of natural marble or onyx marble (onyx stone), polychrome artificial stone-like material with degree of depth.
Technical scheme 4 described preparing artificial stone appear material owing to be in the operation that forms stratum basale with cast utensil cast decorative pattern, therefore, can form various patterns by the variation of injection port bore or pouring speed.
Technical scheme 5 described preparing artificial stone are owing to be in forming the operation of stratum basale, and the mixing that color does not merge degree is carried out on the border that resin material and decorative pattern appear between the material, therefore, can form gyrate figure line.
Technical scheme 6 described preparing artificial stone are owing to have multiple decorative pattern and appear material, can be undertaken paintedly respectively by variant tinting pigment, thus, can obtain more to approach the style of natural marble or onyx marble (onyx stone).
Therefore technical scheme 7 described preparing artificial stone, can make the moulded product completely solidified because its moulded product is to carry out regelate in process furnace.
Therefore technical scheme 8 described preparing artificial stone, can process the moulded product that obtains having different shape because the processing of its moulded product is to be processed as certain thickness for veneer sheet.In addition, therefore finished surface coated surfaces unsaturated polyester resin for coating, can get gloss in molded article surface.
Description of drawings
Fig. 1 is the explanatory view of the preparing artificial stone of the present invention the 1st embodiment.
Fig. 2 is the explanatory view of the pressure method that the stratum basale of veneer sheet pressurizeed in the above-mentioned manufacture method.
Fig. 3 is the explanatory view with the moulded product of above-mentioned manufacture method manufacturing.
Fig. 4 is the explanatory view to the tables after processing with the moulded product of above-mentioned manufacture method manufacturing.
Fig. 5 is the explanatory view of the preparing artificial stone of the present invention the 2nd embodiment.
Fig. 6 is the explanatory view with the moulded product of this manufacture method manufacturing.
Fig. 7 is the explanatory view of the preparing artificial stone of the present invention the 3rd embodiment.
Fig. 8 is for appearing the explanatory view that the injection molding of material is poured into a mould with decorative pattern in this manufacture method.
Embodiment
Below, with reference to accompanying drawing, do an explanation with regard to the specific embodiment of the present invention, for the understanding of the present invention.
Here, Fig. 1 is the explanatory view of the preparing artificial stone of the present invention the 1st embodiment, Fig. 2 is the explanatory view of the pressure method that the stratum basale of veneer sheet pressurizeed in the above-mentioned manufacture method, Fig. 3 is the explanatory view that utilizes the moulded product of above-mentioned manufacture method manufacturing, Fig. 4 is the explanatory view of the tables after the moulded product that utilizes above-mentioned manufacture method manufacturing is processed, Fig. 5 is the explanatory view of the preparing artificial stone of the present invention the 2nd embodiment, Fig. 6 is the explanatory view that utilizes the moulded product of this manufacture method manufacturing, Fig. 7 is the explanatory view of the preparing artificial stone of the present invention the 3rd embodiment, and Fig. 8 is the explanatory view that the injection molding that utilizes the decorative pattern of this manufacture method to appear material is poured into a mould.
At first, with reference to accompanying drawing 1～3, just the preparing artificial stone of the present invention the 1st embodiment describes.
(the 1st operation)
By having on molded 10 that the float glass that is about 8～10mm left and right thickness constitutes, coating in advance becomes the demoulding of moulded product 15 to be easy to not shown releasing agent on the inside bottom surface 13 of molding box 12 and inboard vertical surface 14, and above-mentioned molding box is with the wall material 11 frameworks formation as the vinylchlorid of hard resin material one example of the about 3mm of thickness.Then, transparent top coat is applied to thickness with unsaturated polyester resin and is about 0.5mm.Here, so-called transparent, comprise that inside can have an X-rayed the situation of seeing this degree, how much having color.
Again, molding box 12 forms, and makes size (vertical 600mm, horizontal 1000mm, thick 30mm) measure-alike of the moulded product 15 (finished product) of its inside dimensions and manufacturing.Again, but molded 10 size forms the degree of framework wall material 11, for example, and vertical 620mm, laterally 1200mm.In addition, for increasing the intensity of molding box 12, supporting material 16 (for example, thermoplastic adhesive) is filled in the outer lower portion of wall material 11.
(the 2nd operation)
Solidify with unsaturated polyester resin at top coat, form after the top coat 17, relative unsaturated polyester resin 100 weight parts, allocate micro mist 200～400 weight parts, solidifying agent 0.4～3.5 weight part and the appropriate colouring pigment of shrinking agent 10～40 weight parts, inanimate matter stopping composition into, sizing material (base compound) is refined in joining that the resin material a that making obtains by passing through stir process and vacuum defoamation to handle forms.Here, as unsaturated polyester resin, use the polycondensate of toxilic acid and ethylene glycol, add styrene monomer, use viscosity is 250～500mPas (pascal second), for example, and the resin of 400mPas.Shrinking agent uses methyl methacrylate.Inanimate matter packing material micro mist uses median size at 65 μ m, whiteness in the aluminium hydroxide more than 90 and median size at 300 μ m, whiteness at the lime carbonate more than 90 with weight ratio blended mixture.
Solidifying agent uses the methylethyl ketone peroxide as 55% concentration of ketone peroxide, also allocates the naphthoic acid cobalt as 1% concentration of curing catalyst one example into.Tinting pigment uses the polyester pigment of commercially available white, and unsaturated polyester resin 100 weight parts are allocated 0.04～5.0 weight part into relatively.As be used commercially available polyester defoamer, but then effectively eliminate the air of bringing into when stirring in the short period of time, the preferred use.
Here,, can use rotary type mixing machine, be about 10 minutes stirring and deaeration, make resin a as mixing machine one example as the device that it is stirred.If use rotary type mixing machine with automatic turn over function, then owing to can mix fully at short notice, therefore preferred the use, the velocity of rotation of mixing machine is advisable about with 60rpm.Can prevent from resin material a, to form pin hole by the deaeration processing.Unsaturated polyester resin is added solidifying agent, carry out thorough mixing, then in unsaturated polyester resin, cause polyreaction, slowly solidify, become the hard state.
Fish for an amount of refining sizing material of joining with the thin spoon of stainless steel, the thin spoon of upset, to join the refining sizing material places in the molding box 12, should operate repeatedly, the inside bottom surface 13 of landfill molding box 12 seamlessly, draw rule (chi) to carry out the smoothing processing to joining refining sizing material upper surface with glass or stainless steel making sheet shape again, finally forming specific thickness from the bottom surface of molding box 12 is the stratum basale 18 of 6～15mm, for example 7mm.In addition, also, join the refining sizing material, handle, form stratum basale 18 with drawing rule that its upper surface is carried out smoothing with the cast of cast utensil.
(the 3rd operation)
The veneer sheet (for example, hard rubber sheet) 19 that can leave in the molding box 12 of packing into gap and have a thickness of slab corresponding with finished product thickness is stated from the stratum basale 18.Veneer sheet 19 uses as the veneer sheet of thickness as 16mm, long 570mm, wide 970mm, so that each face lays respectively at 8～15mm inboard of the face corresponding with the outside of moulded product 15.
As shown in Figure 2, for veneer sheet 19 is crimped on the stratum basale 18, the form of the wall material of putting with cross-over connection molding box 12 subtends 11 disposes many, for example 10 stainless steel square tubes 20 at certain intervals.Again, for the distance from the upper surface of moulded product 15 to veneer sheet 19 upper surfaces is made as 7mm, the stainless steel of mounting thickness 7mm is neutralized tight material 21 on veneer sheet 19, for example, iron weight 22 mountings of weight 10～15kg is pressurizeed above square tube 20.Thus, can be with veneer sheet 19 horizontal positioned, and have the gap of certain distance with molding box 12 upper ends.(for example, 15～30 ℃) placed 20～90 minutes at normal temperatures, and along with the unsaturated polyester resin solidified while, veneer sheet 19 is pressed on the stratum basale 18.Thereafter, remove square tube 20, push material 21, and weight 22.
(the 4th operation)
On reach around the above-mentioned veneer sheet 19, casting resin material a is until the upper surface of molding box 12.
(the 5th operation)
Solidified at normal temperatures about 4～15 hours, and behind the formation resin layer 23, carried out the demoulding (with reference to Fig. 3) from 12 pairs of moulded products of molding box 15.Owing on the inside bottom surface 13 of molding box 12 and inboard vertical surface 14, be coated with releasing agent in advance, so the demoulding of moulded product 15 is easy.
Below, with reference to Fig. 4, the desk 25 after the moulded product 15 of the preparing artificial stone manufacturing that utilizes the present invention's one example processed describes.
At first, chamfer machining is carried out at angle to moulded product 15, make from veneer sheet 19 leave decide thickness, 6～15mm for example, promptly around veneer sheet 19, guarantee the resin layer of 6～15mm, coated surfaces unsaturated polyester resin for coating on the finished surface after removing top coat 17 forms table top 26 again.Also have, in the bottom of table top 26, the tabular fixed part 28 that is situated between and holds table top 26 to carry is provided with a plurality of pin being used for supporting table 26,2 platform pin 27 for example.In addition, screw togather many wood screws 29 from the bottom of fixed part 28 to veneer sheet 19, fixed mesa 26 makes desk 25.
Below, with reference to Fig. 5 and Fig. 6, just the preparing artificial stone of the present invention the 2nd embodiment is done an explanation.Compose with same-sign about the artificial stone-like material's identical structure important document, omit it and describe (following embodiment too) in detail with the 1st embodiment.
(the 1st operation)
(the 2nd operation)
After top coat is solidified to form top coat 17 with unsaturated polyester resin, make resin material a, and identical with resin material a composition material and use only be the different color of tinting pigment, for example tawny decorative pattern appears material b.Again, be used in unsaturated polyester resin that decorative pattern appears material b preferably, its viscosity is higher than the viscosity of the unsaturated polyester resin that is used in resin material a, makes color that decorative pattern appears material b not mix with the color of resin material a.
Resin material a and decorative pattern are appeared material b mix, be mixed to the degree that its two color is not merged, that is, color is not mixed to the degree that becomes other colors; Blended is joined the refining sizing material molding box 12 of packing into, and seamlessly landfill is in the inside bottom surface 13 of molding box 12 with thin spoon, and with drawing rule to carry out smoothing and handle joining refining sizing material upper surface, final formation is the stratum basale 30 of thick 7mm for example again.Again, in forming the operation of stratum basale 30, also can hybrid resin material a and decorative pattern appear the degree that border to the color of material b does not merge, form the swirl shape decorative pattern.Also can when making resin material a and decorative pattern and appear material b, add defoamer.
(the 3rd operation)
The veneer sheet 19 that can leave in the molding box 12 of packing into gap and have a thickness of slab corresponding with finished product thickness is stated from the stratum basale 30.As embodiment 1, veneer sheet 19 is pressed on the stratum basale 30.When veneer sheet 19 is pressurizeed, make veneer sheet 19 vibrations as using vibrator, but then resin material a and decorative pattern appear material b natural fusion, expose the degree of depth, therefore preferred the use.
(the 4th operation)
On reach around the above-mentioned veneer sheet 19, will join refining sizing material (resin material a and decorative pattern appear the mixture of material b) cast, until the upper surface of molding box 12.In addition, also can replace and join the refining sizing material, casting resin material a.
(the 5th operation)
Solidified at normal temperatures about 4～15 hours, behind the formation resin layer 32, from molding box 12 demoulding moulded products 31 (with reference to Fig. 6).
Because inside bottom surface 13 and inboard vertical surface 14 at molding box 12 are coated with releasing agent, the demoulding of moulded product 31 is easy.The proportion of moulded product 31 is 1.0～1.1 light weight, and is not easy to crack.Further, moulded product 31 carries out the regelate of 30～50 ℃, 3～4 hours heat treated in process furnace, make the unsaturated polyester resin completely solidified.In the molding box 12 in the moulded products 31 of configuration, the face that is formed by top coat 17 that is in the bottom this moment becomes the upper surface (surface) of moulded product.
Below, with reference to Fig. 7 and Fig. 8, just the preparing artificial stone of the present invention the 3rd embodiment is done an explanation.
(the 1st operation)
To after the inside bottom surface 13 and inboard vertical surface 14 release agent application of the molding box 12 that forms, transparent top coat being applied to thick about 0.5mm that is with unsaturated polyester resin at molded 10 upper framework wall material 11.Be to strengthen the intensity of wall material 11, with pack into the outer lower portion of wall material 11 of supporting material 16.
(the 2nd operation)
Solidify with unsaturated polyester resin at top coat, form after the top coat 17, make resin material a, and decorative pattern appears material b.As shown in Figure 8, store the casting utensil 36 that decorative pattern appears the nozzle 35 that is provided with on the container 34 of material b and the container 34, decorative pattern is appeared on the inside bottom surface that material b injects molding box 12 with having.The bore of the relief outlet 37 of the nozzle 35 by changing cast utensil 36, or the pouring speed (velocity of discharge) that makes decorative pattern appear material b changes, and can make various floral designs.
Secondly, with the resin material a molding box 12 of packing into, with the thin spoon inside bottom surface of landfill molding box 12 seamlessly, with drawing rule to carry out smoothing and handle joining refining sizing material upper surface, final formation is the stratum basale 38 of thick 7mm for example again.In forming the operation of stratum basale 38, also can approach the border that agitating resin material a such as spoon and decorative pattern appear material b, formation swirl shape decorative pattern again.Also can when making resin material a and decorative pattern and appear material b, add defoamer.
(the 3rd operation)
(the 4th operation)
On reach around the above-mentioned veneer sheet 19, casting resin material a is until the upper surface of molding box 12.In addition, can replace resin material a,, add resin material a and decorative pattern respectively and appear material b as stratum basale 38.
(the 5th operation)
Solidified at normal temperatures about 4～15 hours, behind the formation resin layer 32a, from molding box 12 demoulding moulded products 39.Because be coated with releasing agent on the inside bottom surface 13 of molding box 12 and inboard vertical surface 14, the demoulding of moulded product 39 is easy.The proportion of moulded product 39 is 1.0～1.1 light weight, and is not easy to crack.In addition, moulded product 39 carries out the regelate of 30～50 ℃, 3～4 hours heat treated in process furnace, make the unsaturated polyester resin completely solidified.In the moulded product 39 of configuration, the face that is formed by top coat 17 that be in the bottom this moment becomes moulded product upper surface (surface) in the molding box 12.
The present invention is not limited to above-mentioned example, can have some change in the scope that does not break away from main points of the present invention.For example, make up part or all of above-mentioned each embodiment and variation example,, also be contained in the claim scope of the present invention to constitute the occasion of preparing artificial stone of the present invention.
For example, in the preparing artificial stone of the foregoing description, be to form molded with float glass with thickness, but also applicable stainless steel plateform.On molded platform, be to have used the wall material framework shape shaping box of the polyvinyl chloride of hard resin material one example, but also can use the high humidity synthetic resins material and the float glass of polyvinyl resin etc. to form the wall material again.In addition, molding box forms to overlook and is the orthogonal shape, but also can form in the above Polygons of square, trilateral, pentagon, circle, the ellipse any one, also can make the combination of these shapes.Use the hard resin material to form the occasion of wall material, also, its outside is formed by the glued board of thin plate, its inboard hard resin material of can fitting.
Unsaturated polyester resin, shrinking agent, inanimate matter stopping composition, solidifying agent and tinting pigment can use the material except that above-mentioned explanation respectively.It is only to have formed a kind of by a kind of color that decorative pattern appears material, but also can use different tinting pigments, make chromatic multiple decorative pattern and appear material, use above-mentioned materials to form the artificial stone-like material, make the style that more approaches natural marble and onyx stone (onyx marble).In addition, more than be to carry out chamfered, make and leave certain thickness for veneer sheet and process, again at finished surface coated surfaces unsaturated polyester resin for coating forming tabular moulded product bight, but also can apply these resins, leave certain thickness for veneer sheet and process.
[explanation of symbol]
10: molded, 11: the wall material, 12: molding box, 13: inside bottom surface, 14: inboard vertical plane, 15: mechanograph, 16: supporting material, 17: face coat, 18: basalis, 19: laminate, 20: square tube, 21: compress material, 22: Weight, 23: resin bed, 25: desk, 26: table top, 27: platform pin, 28: fixed part, 29: wood screw, 30: base Bottom, 31: mechanograph, 32,32a: resin bed, 34: container, 35: nozzle, 36: the cast utensil, 37: outlet, 38: basalis, 39: mechanograph.
Claims (8)
1. a preparing artificial stone is characterized in that, described manufacture method comprises the operation of following (1)～(5):
(1) pre-prepd, by having on the molded platform that certain thickness float glass or stainless steel plateform constitute, the operation of coated surfaces unsaturated polyester resin for coating on the inside bottom surface of the molding box that forms by the wall material framework that uses float glass or hard resin material and inboard vertical surface;
(2) after described top coat solidifies with unsaturated polyester resin, to put into described molding box by the refining sizing material of joining that resin material is formed, form the operation of the stratum basale of specific thickness, described resin material is the unsaturated polyester resin of relative 100 weight parts, allocate micro mist 200～400 weight parts, solidifying agent 0.4～3.5 weight part and the appropriate colouring pigment of shrinking agent 10～40 weight parts, inanimate matter stopping composition into, stir and deaeration is handled and got;
(3) can leave and pack into gap in the described molding box and be stated from operation on the described stratum basale with the veneer sheet of products thickness respective thickness;
(4) on reach around the described veneer sheet, pour into a mould the operation of described resin material until the molding box upper surface;
(5) after described resin material solidifies at normal temperatures,, obtain proportion and be 1.0～1.1 light weight, be difficult for the operation of rimose moulded product from the described molding box demoulding.
2. a preparing artificial stone is characterized in that, described manufacture method comprises the operation of following (1)～(5):
(1) pre-prepd, by having on the molded platform that certain thickness float glass or stainless steel plateform constitute, the operation of coated surfaces unsaturated polyester resin for coating on the inside bottom surface of the molding box that forms by the wall material framework that uses float glass or hard resin material and inboard vertical surface;
(2) after described top coat solidifies with unsaturated polyester resin, to join the refining sizing material and put into described molding box, form the operation of the stratum basale of specific thickness, the described refining sizing material of joining is with (a) relative unsaturated polyester resin 100 weight parts, allocate shrinking agent 10～40 weight parts into, micro mist 200～400 weight parts of inanimate matter stopping composition, solidifying agent 0.4～3.5 weight part and an amount of tinting pigment, stir and deaeration is handled and the resin material that obtains, (b) relative unsaturated polyester resin 100 weight parts, cooperate shrinking agent 10～40 weight parts, micro mist 200～400 weight parts of inanimate matter stopping composition, solidifying agent 0.4～3.5 weight part and an amount of and tinting pigment described tinting pigment different colours, stir and deaeration is handled and the decorative pattern that obtains appears material, be mixed to the degree that color do not merge and form;
(3) can leave and pack into gap in the described molding box and be stated from operation on the described stratum basale with the veneer sheet of products thickness respective thickness;
(4) on reach around the described veneer sheet, pour into a mould described resin material or described operation of joining the refining sizing material until the molding box upper surface;
(5) after described resin material solidifies at normal temperatures,, obtain proportion and be 1.0～1.1 light weight, be difficult for the operation of rimose moulded product from the described molding box demoulding.
3. a preparing artificial stone is characterized in that, described manufacture method comprises the operation of following (1)～(5):
(1) pre-prepd, by having on the molded platform that certain thickness float glass or stainless steel plateform constitute, the operation of coated surfaces unsaturated polyester resin for coating on the inside bottom surface of the molding box that forms by the wall material framework that uses float glass or hard resin material and inboard vertical surface;
(2) after described top coat solidifies with unsaturated polyester resin, with (a) relative unsaturated polyester resin 100 weight parts, allocate shrinking agent 10～40 weight parts into, micro mist 200～400 weight parts of inanimate matter stopping composition, solidifying agent 0.4～3.5 weight part and an amount of tinting pigment, stir and deaeration is handled and the resin material that obtains, (b) relative unsaturated polyester resin 100 weight parts, allocate shrinking agent 10～40 weight parts into, micro mist 200～400 weight parts of inanimate matter stopping composition, solidifying agent 0.4～3.5 weight part and an amount of and tinting pigment described tinting pigment different colours, stir and deaeration is handled and the decorative pattern that obtains appears material, form in the molding box of seamlessly packing into to have the operation that reaches the stratum basale of specific thickness from the inside bottom surface of described molding box;
(3) can leave and pack into gap in the described molding box and be stated from operation on the described stratum basale with the veneer sheet of products thickness respective thickness;
(4) on reach around the described veneer sheet, pour into a mould described resin material or decorative pattern and appear the operation of material until the molding box upper surface;
(5) after described resin material solidifies at normal temperatures,, obtain proportion and be 1.0～1.1 light weight, be difficult for the operation of rimose moulded product from the described molding box demoulding.
4. preparing artificial stone as claimed in claim 3 is characterized in that, in the formation operation of described stratum basale, it is to be poured into a mould by the cast utensil to form that described decorative pattern appears material.
5. as each described preparing artificial stone in the claim 2～4, it is characterized in that, in the formation operation of described stratum basale, the border that described resin material and described decorative pattern appear between the material is mixed with the degree that color does not merge.
6. as each described preparing artificial stone in the claim 2～5, it is characterized in that described decorative pattern appears material to be had multiplely, is composed with colour by different tinting pigment respectively.
7. as each described preparing artificial stone in the claim 1～6, it is characterized in that described moulded product carries out regelate in process furnace.
8. as each described preparing artificial stone in the claim 1～7, it is characterized in that, described moulded product be processed into and described veneer sheet between leave specific thickness, also on finished surface, be coated with the top coat vibrin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004087177 | 2004-03-24 | ||
| JP2004087177 | 2004-03-24 |
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| CN1673164A true CN1673164A (en) | 2005-09-28 |
| CN100391888C CN100391888C (en) | 2008-06-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200410058921XA Expired - Fee Related CN100391888C (en) | 2004-03-24 | 2004-07-21 | Method for producing artificial stone |
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| CN (1) | CN100391888C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010103535A2 (en) * | 2009-02-20 | 2010-09-16 | Gosakan Aravamudan | In situ foaming in artificial stone |
| CN103496883A (en) * | 2013-09-26 | 2014-01-08 | 吴火福 | Marble imitating substrate and preparation method thereof |
| CN103788314A (en) * | 2014-02-13 | 2014-05-14 | 浙江省乐清树脂厂 | Rapid-prototyping high-performance imitation natural marble series mould plastic |
| CN105384390A (en) * | 2015-12-01 | 2016-03-09 | 广州市奥维装饰材料有限公司 | Quartz stone board and preparation method thereof |
| CN110065140A (en) * | 2019-04-26 | 2019-07-30 | 张万勇 | A kind of cast mineral method of surface finish |
| TWI739282B (en) * | 2019-01-30 | 2021-09-11 | 日商松下知識產權經營股份有限公司 | Method for manufacturing resin molded product and resin molded product |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85109513A (en) * | 1985-12-31 | 1987-07-08 | 钱平吉 | The manufacturing process of composite intensified TERRAZZO |
| CN1137016C (en) * | 2001-01-18 | 2004-02-04 | 梅县龙盘新型建材有限公司 | Artificial slate making process |
-
2004
- 2004-07-21 CN CNB200410058921XA patent/CN100391888C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010103535A2 (en) * | 2009-02-20 | 2010-09-16 | Gosakan Aravamudan | In situ foaming in artificial stone |
| WO2010103535A3 (en) * | 2009-02-20 | 2010-11-04 | Gosakan Aravamudan | Structure for door or other furniture |
| US8613978B2 (en) | 2009-02-20 | 2013-12-24 | Gosakan Aravamudan | In situ foaming in artificial stone |
| CN103496883A (en) * | 2013-09-26 | 2014-01-08 | 吴火福 | Marble imitating substrate and preparation method thereof |
| CN103496883B (en) * | 2013-09-26 | 2015-09-23 | 吴火福 | A kind of parian substrate and preparation method thereof |
| CN103788314A (en) * | 2014-02-13 | 2014-05-14 | 浙江省乐清树脂厂 | Rapid-prototyping high-performance imitation natural marble series mould plastic |
| CN105384390A (en) * | 2015-12-01 | 2016-03-09 | 广州市奥维装饰材料有限公司 | Quartz stone board and preparation method thereof |
| TWI739282B (en) * | 2019-01-30 | 2021-09-11 | 日商松下知識產權經營股份有限公司 | Method for manufacturing resin molded product and resin molded product |
| CN110065140A (en) * | 2019-04-26 | 2019-07-30 | 张万勇 | A kind of cast mineral method of surface finish |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100391888C (en) | 2008-06-04 |
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