CN109305774A - Artificial stone and preparation method thereof - Google Patents
Artificial stone and preparation method thereof Download PDFInfo
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- CN109305774A CN109305774A CN201811347908.4A CN201811347908A CN109305774A CN 109305774 A CN109305774 A CN 109305774A CN 201811347908 A CN201811347908 A CN 201811347908A CN 109305774 A CN109305774 A CN 109305774A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/18—Polyesters; Polycarbonates
-
- 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
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
- B29C67/242—Moulding mineral aggregates bonded with resin, e.g. resin concrete
- B29C67/243—Moulding mineral aggregates bonded with resin, e.g. resin concrete for making articles of definite length
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/06—Acrylates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of artificial stones and preparation method thereof, belong to artificial stone technical field.The artificial stone is mainly prepared by the raw material of following weight part ratio: modified 60~85 parts of mixture, 0~45 part of aggregate, 9.5~34.7 parts of resin, 0.05~0.15 part of curing agent, 0~0.05 part of promotor, the modifying agent is selected from: at least one of titante coupling agent and Borate Ester as Coupling.The artificial stone chooses titanate ester, Borate Ester as Coupling is modified artificial stone aggregate and powder as modifying agent, improves the compatibility of the inorganic matters and resin such as aggregate, powder.The modified oil factor that can effectively reduce aggregate and powder reduces the amount of resin in artificial stone production process, improves the bond strength of resin and aggregate, powder, enhances the mechanical property of artificial stone, this method of modifying is easy to operate, and effect is obvious.
Description
Technical field
The present invention relates to artificial stone technical fields, more particularly to a kind of artificial stone and preparation method thereof.
Background technique
The stone material that China has become the first in the world produces and sells and big export country.Early stage is mainly with the side for digging mine of cutting into a mountain
Formula exploitation and then is processed into product at quarry stone, on the one hand because its lumber recovery it is low caused by resource waste；On the other hand, with excessively opening
It adopts, the price of lithotome constantly increases, and the application of lithotome and development is made to receive obstruction.
With the rise of artificial stone, the sustainable development of Ornamental Stone Industry is guaranteed.The alternative natural stone of artificial stone
The certain applications and function of material, and have many advantages, such as benefit useless, energy-saving and environmental protection, inexpensive, gradually it is taken seriously in building trade.
Wherein, high praise of the resin type artificial stone because of the advantages that its intensity is high, color decorative pattern good simulation by consumer.
But artificial stone still remains problems in production, use process: first is that resin content height causes to be produced into
This height；Second is that resin type artificial stone thermal expansion coefficient is too big, heat distortion temperature is low.If can solve the above problem, can effectively open up
The application range and market scale of artificial stone are opened up, bigger value is created.
Summary of the invention
Based on this, it is necessary in view of the above-mentioned problems, a kind of artificial stone is provided, amount of resin used in the artificial stone
Few, plate thermal expansion coefficient is low, and plate body mechanical strength with higher.
A kind of artificial stone is mainly prepared by the raw material of following weight part ratio:
The modified mixture is prepared by the raw material of following weight part ratio:
The modifying agent is selected from: at least one of titante coupling agent and Borate Ester as Coupling.
Above-mentioned artificial stone, is first modified powder and aggregates --- use modifying agent and powder, part bone
Material chemically reacts, and in the functional groups such as the long alkane chain of its surface grafting or amino, double bond, aggregate and powder is made to become thin from hydrophilic
Water obtains modified mixture；Modified mixture (i.e. modified aggregate and powder) is recycled to prepare high-performance artificial stone.Because thin
Aggregate and powder have large specific surface area and oil factor, and oil factor can be significantly reduced by being surface-treated to it, reduce resin
Dosage can also enhance the bond strength of aggregate, powder and resin, improve the mechanical strength of plate and reduce its coefficient of expansion.
And the selection for modifying agent, the present inventor select titante coupling agent and boric acid after comparing by largely screening
Esters coupling agent can directly react with aggregate and powder after dilution without hydrolysis, and modified effect is good and simple process, with compared with
Big advantage.And for the weight part ratio of aggregate and powder in the modified mixture, it can be chosen according to specific demand different
Proportion.
The aggregate is selected from the aggregate that partial size is 50~120 mesh in one of the embodiments,；The powder is selected from partial size
For the powder of 300-400 mesh.Aggregate and the powder cooperation for selecting above-mentioned partial size, have preferable resultant effect.
The aggregate is selected from one of the embodiments: at least one of quartz, calcium carbonate and aluminium hydroxide；
The powder is selected from: at least one of quartz, calcium carbonate and aluminium hydroxide.
The resin is selected from one of the embodiments: unsaturated polyester resin, acryl resin, epoxy resin, third
At least one of olefin(e) acid resin and polyurethane resin；
The curing agent is selected from: azo-bis-isobutyl cyanide, methyl ethyl ketone peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide,
At least one of diethyl dioxide hecanoic acid t-butyl ester.
The promotor is selected from one of the embodiments: the organic salt of manganese systems metal, cobalt iso-octoate, in mercaptan
At least one；The organic solvent is selected from: at least one of ethyl alcohol, ethylene glycol, acetone, methylene chloride.It should be understood that
Organic solvent can dissolve modifying agent, still, select above-mentioned organic solvent, with it is at low cost, be easy to get, easy to operate excellent
Point.
For promotor, if reaction speed need to be accelerated or reduce solidification temperature addition promotor may be selected, for different
The matched promotor of addition may be selected in curing agent.
The invention also discloses the preparation methods of above-mentioned artificial stone, comprising the following steps:
It prepares modified mixture: the raw material of the modified mixture is uniformly mixed, heating reaction obtains modified mixture；
Stock: above-mentioned modified mixture is uniformly mixed with remaining raw material, obtains artificial stone pug；
Press curing: above-mentioned artificial stone pug is imported into mold, is heating and curing after compacting to get artificial stone.
Above-mentioned preparation method has the advantages that simple process, bad to equipment requirement, is suitable for industrialized popularization and application.
In one of the embodiments, in the modified mixture step of the preparation, is flowed back with 70-95 DEG C, be stirred to react 20-
40min.The reaction time can suitably be reduced by improving temperature, but temperature is excessively high may cause certain coupling agents containing specific groups and become
Property, reaction efficiency is too low if too low, and required time is too long, after groping repeatedly, the inventors discovered that anti-with above-mentioned condition
There should be preferable effect.
In one of the embodiments, in the modified mixture step of the preparation, after reaction by product at 85-95 DEG C
Lower drying.
In one of the embodiments, in the press curing step, with the progress of vacuum pressing mode, pressing conditions 3-
5MPa vibration compacting 0.5-2min.
In one of the embodiments, in the press curing step, the condition of cure are as follows: 50-80 DEG C of solidification 3-4h.
Inventive principle: the present inventor summarizes discovery, common artificial stone raw materials such as quartz, calcium carbonate, hydrogen under study for action
Aluminium oxide is all inorganic matter, and surface hydrophilic is difficult to be infiltrated by organic polymer.Therefore it can make its table by being modified to it
Face is hydrophobic from the hydrophilic part that becomes, it is made to be easier to be coated by resin.And feed particles are thinner, specific surface area is bigger, and oil factor is just
It is higher；Meanwhile the activity hydroxy number on surface is also more, it is easier to be chemically reacted.Accordingly, the present invention chooses artificial stone and matches
The higher fine grained aggregate of oil factor and powder in side, are chemically reacted using modifying agent with it, in surface grafting amino, double
The groups such as key or Long carbon chain, can effectively reduce the oil factor of aggregate and powder, improve its compatibility with resin.
And common coupling agent such as silane coupling agent generate silanol after needing to hydrolyze and body surface hydroxyl generation chemistry is anti-
It answers, and need to use as early as possible to prevent it from reacting to each other and generate silicon ball, to the more demanding of production technology and equipment；In contrast,
Titanate coupling agent and boric acid ester coupler can directly be reacted with aggregate and powder after dilution without hydrolysis, modified effect it is good and
Simple process has greater advantage.
When preparing artificial stone, modified aggregate, powder and unmodified aggregate are mixed, then with resin/curing agent system into
Row mixing enters molding after mixing evenly and makes and be heating and curing.In the curing process, the carboxyl of resinous terminal can with modified aggregate and
The amino of powder surface reacts；Double bond in resin can be reacted with the double bond of modified aggregate and powder surface；Resin chain can with change
Property aggregate and powder surface Long carbon chain tangle；The bond strength of resin and aggregate, powder can be improved by above-mentioned means, increase
The mechanical property of strong plate body, avoid aggregate, powder because not causing artificial stone plate to occur falling off by resin infiltration, hickie etc. shows
As.Meanwhile because modifying process reduces the oil factor of aggregate and powder, can be infiltrated using less resin, effectively
The production cost for reducing artificial stone.Compared with quartz, the thermal expansion coefficient of resin is larger, by raw material be modified come
The dosage for reducing resin in production process can reduce the thermal expansion coefficient of artificial stone finished product.
Compared with prior art, the invention has the following advantages:
A kind of artificial stone of the invention chooses titanate ester, Borate Ester as Coupling as modifying agent to artificial stone bone
Material and powder are modified, and improve the compatibility of the inorganic matters and resin such as aggregate, powder.It is modified to can effectively reduce aggregate and powder
The oil factor of body reduces the amount of resin in artificial stone production process, improves the bond strength of resin and aggregate, powder, enhancing
The mechanical property of artificial stone, this method of modifying is easy to operate, and effect is obvious.
The preparation method of artificial stone of the invention a kind of, selected modifying agent is compared with common silane coupling agent, nothing
It needs to hydrolyze, can directly be reacted with aggregate after dilution, simple process is not high to equipment requirement.And the preparation flow of the artificial stone
Have the advantages that step is few, simple process, is suitable for industrialized popularization and application.
Specific embodiment
To facilitate the understanding of the present invention, below with reference to embodiment to invention is more fully described.But this hair
It is bright to realize in many different forms, however it is not limited to embodiment described herein.On the contrary, providing these embodiments
Purpose be to make the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
Raw materials used following embodiment is commercially available.
Embodiment 1
A kind of artificial stone is prepared by the raw material of following weight part ratio:
Modified mixture
Above-mentioned artificial stone is prepared by the following method to obtain:
1, modified mixture is prepared:
0.4 part of KR-TTS is weighed by formula, adds 10 parts of methylene chloride dissolutions, adds 40 part of 400 mesh silica flour, 90 DEG C are returned
It is dried after stream reaction 30min, obtains modified mixture.
2, it stocks up:
Above-mentioned modified mixture is uniformly mixed with 40 part of 70~120 mesh (average grain diameter is 100 mesh) quartz particle；
9.45 parts of unsaturated polyester resins, 0.1 part of diethyl dioxide hecanoic acid t-butyl ester and 0.05 part of cobalt iso-octoate are weighed by formula, and
It is added into batch mixer and mixes, mixing time 30min；Modified mixture/quartz particles mixture is mixed with resin/curing agent
It closes object and batch mixer is added, stirring obtains artificial stone pug in 10 minutes.
3, press curing:
Completed in compacting tool set groove prevent bonding brown paper, with i.e. by the uniform cloth of artificial stone pug in a groove,
Flat surface, then cover one layer of brown paper；The mold of the good artificial stone pug of cloth is loaded into vacuum vibration press, pressure 4MPa,
Vacuum vibration compacting 1min obtains plate；Plate body demoulding is put on tile floor, transfer, which is sent into baking oven, to be solidified, and 80 DEG C
Constant temperature places 4h；Determine thickness after the completion of solidification and polishes artificial stone finished product to obtain the final product.
By above-mentioned artificial stone finished product according to artificial stone national standard JCT 908-2013 to the phase of the high-performance artificial stone
It closes performance to be detected, obtaining compression strength average value by pressure-proof and snap-resistent loading test is 190.02MPa, compared with standard 150MPa
It is higher by 26.68%；Flexural strength 52.26MPa is higher by 49.33% compared with standard 35MPa；48h water absorption rate is 0.05%, 15d water suction
Rate is 0.06%, complies with standard the requirement of middle water absorption rate < 0.8%, and Mohs' hardness 7, mirror image glossiness is 78 after polishing,
Thermal linear expansion coefficient is 1.6 × 10-5℃-1, middle thermal linear expansion coefficient is complied with standard less than 3.5 × 10-5 DEG C-1Requirement.
Embodiment 2
A kind of artificial stone is prepared by the raw material of following weight part ratio:
Modified mixture
Above-mentioned artificial stone is prepared by the following method to obtain:
1, modified mixture is prepared:
0.3 part of KR-7 is weighed by formula, 10 parts of isopropanols are added, 5min, which is stirred at room temperature, makes it be uniformly dispersed, and is modified
Agent solution needs more modifying agent, therefore, by 3 since 325 mesh Paris whites are than 80 mesh calcium carbonate granule large specific surface areas
Ratio than 7 is divided into two parts；3 part of 325 mesh Paris white and 64.1 part of 80 mesh calcium carbonate granule are weighed by formula, is separately added into 3
It is dried at 90 DEG C after 7 one-tenth modifier solutions, 90 DEG C of back flow reaction 60min, obtains modified mixture.
2, it stocks up:
After mixing by modified 80 mesh calcium carbonate granule and 16 part of 20 mesh calcium carbonate granule, 6.5 parts of insatiable hungers are added
With the mixture of polyester resin and 0.1 part of diethyl dioxide hecanoic acid t-butyl ester, 3 parts of 325 mesh carbon of modification are added in stirring after five minutes
Sour calcium powder continues stirring and obtains artificial stone pug in 5 minutes；
3, press curing:
Completed in compacting tool set groove prevent bonding brown paper, with i.e. by the uniform cloth of artificial stone pug in a groove,
Flat surface, then cover one layer of brown paper；The mold of the good artificial stone pug of cloth is loaded into vacuum vibration press, pressure 4MPa,
Vacuum vibration compacting 1min obtains plate；Plate body demoulding is put on tile floor, transfer, which is sent into baking oven, to be solidified, and 80 DEG C
Constant temperature places 4h；Determine thickness after the completion of solidification and polishes artificial stone finished product to obtain the final product.
By above-mentioned artificial stone finished product according to artificial stone national standard JCT 908-2013 to the phase of the high-performance artificial stone
It closes performance to be detected, obtaining compression strength average value by pressure-proof and snap-resistent loading test is 172.41MPa, compared with standard 150MPa
It is higher by 14.94%；Flexural strength 49MPa is higher by 40.09% compared with standard 35MPa；48h water absorption rate is 0.06%, 15d water absorption rate
It is 0.08%, Mohs' hardness 6, mirror image glossiness is 69 after polishing, and thermal linear expansion coefficient is 1.9 × 10-5 DEG C-1, meet mark
Thermal linear expansion coefficient is less than 4.0 × 10-5 DEG C in standard-1Requirement.
Embodiment 3
A kind of artificial stone is prepared by the raw material of following weight part ratio:
Modified mixture
Above-mentioned artificial stone is prepared by the following method to obtain:
1, it prepares modified mixture: weighing 0.3 part of boric acid ester coupler LD-100P by formula and be dissolved in 9.7 parts of isopropanols, room
Temperature stirring 5min；Weigh 90 DEG C of bakings after 55 part of 2000 mesh aluminium hydrate powder reacts 60min with 90 DEG C of modifier solution mixings
It is dry, obtain modified mixture；
2, it stocks up:
20 parts of polymethyl methacrylate powder and 0.3 part of azo-bis-isobutyl cyanide are added in 14 parts of methacrylic acid monomers and are stirred
Mixing 2h dissolves it sufficiently, and standing overnight makes it empty bubble, obtains resin；Vacuum is added with above-mentioned modified mixture in resin to mix
It is mixed in material machine, control vacuum degree is 0.9~1MPa, and stirring 20min obtains artificial stone pug.
3, press curing:
Completed in compacting tool set groove prevent bonding brown paper, with i.e. by the uniform cloth of artificial stone pug in a groove,
Flat surface, then cover one layer of brown paper；The mold of the good artificial stone pug of cloth is loaded into vacuum vibration press, pressure 4MPa,
Vacuum vibration compacting 1min obtains plate；Plate body demoulding is put on tile floor, transfer, which is sent into baking oven, to be solidified, and 50 DEG C
Constant temperature places 3h；Determine thickness after the completion of solidification and polishes artificial stone finished product to obtain the final product.
By above-mentioned artificial stone finished product according to artificial stone national standard JCT 908-2013 to the phase of the high-performance artificial stone
It closes performance to be detected, obtaining compression strength average value by pressure-proof and snap-resistent loading test is 181.71MPa, compared with standard 150MPa
It is higher by 21.14%；Flexural strength 71.43MPa is higher by 78.57% compared with standard 40MPa；48h water absorption rate is 0.05%, 15d water suction
Rate is 0.07%, Mohs' hardness 6, and mirror image glossiness is 76 after polishing, and thermal linear expansion coefficient is 1.5 × 10-5 DEG C-1,
Middle thermal linear expansion coefficient is complied with standard less than 4.0 × 10-5 DEG C-1Requirement.
Comparative example 1
A kind of artificial stone is prepared using material same as Example 1, and difference is, all raw materials are mixed
After prepare artificial stone pug, then according to the method for embodiment 1 mode press curing produce artificial stone.
By above-mentioned artificial stone finished product according to artificial stone national standard JCT 908-2013 to the phase of the high-performance artificial stone
It closes performance to be detected, obtaining compression strength average value by pressure-proof and snap-resistent loading test is 124.46MPa, compared with standard 150MPa
Low 17.03%；Flexural strength 19.87MPa, low compared with standard 40MPa 50.33%；48h water absorption rate is that 0.11%, 15d water absorption rate is
0.14%, Mohs' hardness 6, mirror image glossiness is 74 after polishing, and thermal linear expansion coefficient is 2.5 × 10-5 DEG C-1, meet
Thermal linear expansion coefficient is less than 4.0 × 10-5 DEG C in standard-1Requirement.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of artificial stone, which is characterized in that be mainly prepared by the raw material of following weight part ratio:
The modified mixture is prepared by the raw material of following weight part ratio:
The modifying agent is selected from: at least one of titante coupling agent and Borate Ester as Coupling.
2. artificial stone according to claim 1, which is characterized in that the aggregate is selected from the bone that partial size is 50~120 mesh
Material；The powder is selected from the powder that partial size is 300-400 mesh.
3. artificial stone according to claim 1, which is characterized in that the aggregate is selected from: quartz, calcium carbonate and hydrogen-oxygen
Change at least one of aluminium；The powder is selected from: at least one of quartz, calcium carbonate and aluminium hydroxide.
4. artificial stone according to claim 1, which is characterized in that the resin is selected from: unsaturated polyester resin, Ya Ke
At least one of power resin, epoxy resin, acrylic resin and polyurethane resin；
The curing agent is selected from: azo-bis-isobutyl cyanide, methyl ethyl ketone peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide, peroxide
Change at least one of diethyl hecanoic acid t-butyl ester.
5. artificial stone according to claim 1, which is characterized in that the promotor is selected from: the organic salt of manganese systems metal
At least one of class, cobalt iso-octoate, mercaptan；The organic solvent is selected from: ethyl alcohol, ethylene glycol, acetone, in methylene chloride extremely
Few one kind.
6. the preparation method of the described in any item artificial stones of claim 1-5, which comprises the following steps:
It prepares modified mixture: the raw material of the modified mixture is uniformly mixed, heating reaction obtains modified mixture；
Stock: above-mentioned modified mixture is uniformly mixed with remaining raw material, obtains artificial stone pug；
Press curing: above-mentioned artificial stone pug is imported into mold, is heating and curing after compacting to get artificial stone.
7. the preparation method of artificial stone according to claim 6, which is characterized in that the modified mixture step of the preparation
In, it is flowed back with 70-95 DEG C, is stirred to react 20-60min.
8. the preparation method of artificial stone according to claim 7, which is characterized in that the modified mixture step of the preparation
In, product is dried at 85-95 DEG C after reaction.
9. the preparation method of artificial stone according to claim 6, which is characterized in that in the press curing step, with
Vacuum pressing mode carries out, and pressing conditions is 3-5MPa vibration compacting 0.5-2min.
10. the preparation method of artificial stone according to claim 6, which is characterized in that in the press curing step, institute
State condition of cure are as follows: 50-80 DEG C of solidification 3-4h.
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| CN112694283A (en) * | 2021-01-20 | 2021-04-23 | 清远金谷智联环保产业研究院有限公司 | Artificial stone and method for preparing artificial stone by utilizing solid hazardous wastes |
| CN113213810A (en) * | 2021-05-20 | 2021-08-06 | 福建省春天生态科技股份有限公司 | Preparation method of environment-friendly self-luminous artificial stone |
| CN113213810B (en) * | 2021-05-20 | 2022-06-10 | 福建省春天生态科技股份有限公司 | Preparation method of environment-friendly self-luminous artificial stone |
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