WO2016041323A1 - 一种由彩色石英砂制作人造彩色石英合成石的方法 - Google Patents

一种由彩色石英砂制作人造彩色石英合成石的方法 Download PDF

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Publication number
WO2016041323A1
WO2016041323A1 PCT/CN2015/073295 CN2015073295W WO2016041323A1 WO 2016041323 A1 WO2016041323 A1 WO 2016041323A1 CN 2015073295 W CN2015073295 W CN 2015073295W WO 2016041323 A1 WO2016041323 A1 WO 2016041323A1
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Prior art keywords
quartz sand
colored quartz
artificial
artificial colored
binder
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PCT/CN2015/073295
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English (en)
French (fr)
Inventor
张清
张敏
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常州明清新材料技术有限公司
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Publication of WO2016041323A1 publication Critical patent/WO2016041323A1/zh

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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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/06—Quartz; Sand
    • 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

Definitions

  • the invention relates to a formula and a preparation method of artificial synthetic stone, in particular to a formula and a preparation method of artificial colored quartz synthetic stone.
  • the Italian synthetic stone manufacturing technology and equipment has the world's advanced level. Italy's Bailitong Company is its outstanding representative. Its synthetic synthetic stone manufacturing technology and technology (hereinafter collectively referred to as “Italian Bailitong Artificial Stone Technology”) are:
  • the stone organic binder can be cured at normal pressure and normal temperature, and does not require heat curing, and does not require energy consumption.
  • large-scale enterprises generally use low-temperature heating to quickly cure products and shorten the production cycle. Due to the low temperature of low temperature heating, the energy consumption is not high, but the economic benefits are considerable.
  • Bailitong artificial stone technology is at the world's leading level. By the end of 2008, it had sold more than 180 production lines of Bailitong synthetic stone equipment worldwide.
  • Italy Bailitong artificial stone technical solution in the coloring method is: the inorganic or organic pigments are dispersed, dissolved in the resin, resin to bond natural stone, stone sand and package coloring. Due to the dispersion, dissolution and compatibility of the colorant and the resin, the relative softness of the resin hardness and other technical factors and technical difficulties, the gloss of the synthetic stone is difficult to increase, the color is single, and the color consistency of each batch and each batch is poor. The problem of low qualified rate of finished products. This aspect of synthetic synthetic stone cannot be compared with natural granite, marble and other stone products before the present invention.
  • the performance parameters that can be achieved by the Bailitong artificial quartz stone products produced by the Italian company, and the performance of the natural stone are:
  • the colored artificial synthetic stone blank after curing generally needs to undergo cutting, grinding, polishing and other processing steps.
  • various pigment waste waters mainly inorganic pigments
  • fine sand and stone powder about 3% of the total weight of the product
  • Fine sand and stone powder are better to handle: if the amount is small, it is generally filtered and dried before being harmlessly landfilled; if the amount is large, it is generally made into building bricks of various shapes, and the waste is recycled and reused.
  • various mixed pigment wastewaters are more difficult to handle.
  • process technologies such as adsorption, sedimentation, filtration and recycling, they can only reduce pollution and barely meet environmental requirements. Solve this environmental problem completely. It has become a very urgent and urgently needed scientific and effective solution to the problem of sustainable development of artificial synthetic stone manufacturing enterprises.
  • the synthetic synthetic stone products can not reach the current high-quality natural marble, granite and other stone in terms of color, gloss, pattern, texture and texture. Performance level.
  • the appearance of the bright and beautiful and beautiful is a very intuitive and important evaluation indicator, it will directly People are judged whether it is high-end, whether it is high-end, etc., which directly affects the price of its sales!
  • color the color of the bright, pure, deep and layered sense can not be expressed or under-performed
  • texture and texture the natural, realistic, texture and diversity of the pattern texture can not be expressed or under-performed
  • An object of the present invention is to provide a method for producing an artificial colored quartz synthetic stone from colored quartz sand, which solves one or more of the above prior art problems.
  • a method of making an artificial colored quartz synthetic stone from colored quartz sand comprising the steps of:
  • the above raw materials are formulated in the following parts by weight: 10 to 30 parts of natural quartz powder, 7 to 20 parts of a binder, and 50 to 85 parts of artificial colored quartz sand.
  • the invention provides a method for preparing artificial colored quartz synthetic stone from colored quartz sand, which uses colored quartz sand as an aggregate, and does not produce various pigment waste water in the processing steps of cutting, grinding and polishing after curing,
  • the invention completely eliminates the production of pigment wastewater from the source, and solves an unresolved road on the sustainable development of artificial synthetic stone manufacturing. technical challenge.
  • the binder is an unsaturated polyester resin (UPR) modified with dicyclopentadiene (DCPD) or a derivative thereof.
  • URR unsaturated polyester resin
  • DCPD dicyclopentadiene
  • UPR o-benzene type and meta-benzene type unsaturated polyester resin
  • St styrene
  • St is prepared by dissolving unsaturated polyester in St., in which St is mainly used for dilution and crosslinking.
  • the invention further optimizes the bonding agent by optimizing the combination of DCPD and its derivatives with UPR to reduce the amount of St.
  • the mechanism is:
  • the chain termination reaction in the DCPD addition method can lower the molecular weight of the UPR and lower the viscosity
  • the UPR modified by DCPD and its derivatives has good comprehensive performance, especially meeting some important indexes required by the stone industry: such as low shrinkage (can be reduced from about 9% before modification to about 3%); water resistance Excellent (can be soaked in water for a long time); high heat resistance (high thermal stability below 200 °C), UV resistance (exposure in the sun for a long time), good chemical resistance, low volatility, product machinery High performance (such as bending strength, etc.).
  • the construction technology is good, the storage period is long, the curing time is short, the bonding strength is high, the gloss is high, and the cost is low.
  • the graft copolymerization of DCPD and St has good affinity, compatibility and mutual compatibility. Since the DCPD molecule contains a plurality of unsaturated double bonds, it is chemically active. DCPD is a terminal blocker. DCPD is added at both ends of the unsaturated polyester molecular chain.
  • the unsaturated double bond on the five-membered ring in the DCPD capping becomes a cross-linking point, participates in the cross-linking reaction, increases the cross-linking density, and thus changes the resin.
  • the volatility and volatilization of St are greatly reduced. According to the actual measurement: the amount of volatilization can be reduced by more than 50% (a rough algorithm: every 1% reduction in St usage, St will be reduced by 5% during the curing phase).
  • the binder is a DCPD modified air dry unsaturated polyester resin, a DCPD modified solvent resistant unsaturated polyester resin, a dicyclopentadienyl acrylate (DCPA) modified unsaturated polyester resin.
  • DCPA dicyclopentadienyl acrylate
  • the natural quartz powder has a particle size of 325 mesh or more
  • the artificial colored quartz sand is a spherical particle group having an unequal shape
  • the particle size distribution of the particle group is a complementary gradation of pores.
  • the particle size distribution of the particle group is complemented by pores, which can greatly improve the physical properties such as compactness, water absorption, freeze-thaw and so on.
  • the artificial colored quartz sand comprises an artificial colored quartz sand coarse aggregate having a particle diameter of 5 to 20 mesh, an aggregate of artificial colored quartz sand of 20 to 80 mesh, and an artificial colored quartz sand fine aggregate of 80 to 200 mesh;
  • the above-mentioned various artificial colored quartz sands are proportioned according to the following parts by weight: 20-40 parts of artificial colored quartz sand coarse aggregate, 40-60 parts of aggregate in artificial colored quartz sand, and 20-40 parts of artificial colored quartz sand fine aggregate. .
  • the particle size distribution of the particle group is complemented by pores, which can greatly improve the physical properties such as compactness, water absorption, freeze-thaw and so on.
  • an auxiliary material of less than 30% by weight of the artificial colored quartz sand is added before the addition of the curing agent, and the auxiliary material is one of transparent quartz sand, transparent cullet, luminous material, metal sheet or A variety of auxiliary materials have a particle size of 5 to 40 mesh.
  • Adding suitable auxiliary materials can enhance the visual beauty of the product, giving the product a beautiful and gorgeous visual experience in the sun.
  • the curing agent is methyl ethyl ketone peroxide (MEKP), cyclohexanone peroxide (CHP), t-butyl peroxy 2-ethylhexanoate (TBPO);
  • the coupling agent is an organosilane coupling agent,
  • the promoter is cobalt naphthenate and cobalt isooctylate;
  • the weight of the curing agent is 0.02% to 0.6% by weight of the binder; the weight of the coupling agent is 0.01% to 0.4% by weight of the binder; and the weight of the accelerator is 0.01% to 0.5% by weight of the binder.
  • the organosilane coupling agent has the general formula RSiX 3 , and the available varieties are: KH-507, KH-1714 of the Chinese Academy of Sciences; KE420, KE340, KE109 of Shin-Etsu Chemical Co., Ltd., Japan.
  • the curing is performed by uniformly mixing a mixture of artificial colored quartz sand, a promoter, a coupling agent, and a curing agent, and pressing and forming the vacuum in a vacuum machine, and then placing it in 150. Curing in a curing oven below °C.
  • the binder further comprises a reactive type of solvent having a weight fraction of 20% to 35%, and the reactive type of the solvent is styrene (St).
  • the physical and chemical properties of the colored quartz sand used in the present invention should conform to GB/T 14684-2011 "Construction Sand”; GB/T 1768 “Test Rotating Rubber Wheel Method for Paint and Varnish Wear Resistance”; JC/ T 753-2001 “Chemical analysis method for siliceous glass raw materials”; JC/T 1071-2008 “Standard sand for asphalt shingles”.
  • the quartz colored sand selected by the invention can be selected in theory as long as it can meet specific physical and chemical indexes, whether artificial colored sand or natural colored sand.
  • the invention provides a method for producing artificial colored quartz synthetic stone from colored quartz sand, comprising the following steps:
  • the natural quartz powder is added to the bonding agent and stirred uniformly; the bonding agent is a DCPD modified air-drying unsaturated polyester resin.
  • the binder also includes a reactive type of solvent having a weight fraction of 30%, and the reactive type of solvent is styrene (St).
  • the natural quartz powder has a particle size of 325 mesh or more.
  • the accelerator is cobalt naphthenate; the amount is 0.2% by weight of the binder.
  • the coupling agent is added and stirred uniformly; the coupling agent is an organosilane coupling agent in an amount of 0.2% by weight of the binder.
  • the curing agent is added and stirred uniformly; the curing agent is methyl ethyl ketone peroxide (MEKP) in an amount of 0.3% by weight of the binder.
  • MEKP methyl ethyl ketone peroxide
  • the curing is a mixture of artificial colored quartz sand, a promoter, a coupling agent, and a curing agent.
  • the curing was press-formed after vacuuming in a vacuum machine, and then solidified in a curing oven at 150 °C.
  • the above raw materials were formulated in the following parts by weight: 20 parts of natural quartz powder, 15 parts of a binder, and 65 parts of artificial colored quartz sand.
  • the artificial colored quartz sand is a spherical particle group with unequal diameters, and the particle size distribution of the particle group is complemented by pores. More specifically, the artificial colored quartz sand comprises an artificial colored quartz sand coarse aggregate having a particle diameter of 5 to 20 mesh, an aggregate of artificial colored quartz sand of 20 to 80 mesh, and an artificial colored quartz sand fine aggregate of 80 to 200 mesh; The artificial colored quartz sand is proportioned according to the following parts by weight: 30 parts of artificial colored quartz sand coarse aggregate, 50 parts of artificial colored quartz sand aggregate, and 30 parts of artificial colored quartz sand fine aggregate.
  • the invention provides a method for preparing artificial colored quartz synthetic stone from colored quartz sand, which uses colored quartz sand as an aggregate, and does not produce various pigment waste water in the processing steps of cutting, grinding and polishing after curing,
  • the invention completely eliminates the production of pigment wastewater from the source and solves an unsolved technical problem on the road of sustainable development in the field of artificial synthetic stone manufacturing.
  • the invention further optimizes the bonding agent, and the modified bonding agent can cross-link with the dissolving agent, reduces the amount of the dissolving agent, and reduces the volatility effect of the dissolving agent, and is more in line with environmental protection requirements.
  • a step closer the particle size distribution of the particle group is complemented by pores, which can greatly improve the physical properties such as compactness, water absorption, freeze-thaw and so on.
  • the bonding agent used in this embodiment is mainly a DCPD modified air-drying unsaturated polyester resin.
  • the experimental data of the DCPD modified air-drying UPR with the content of 85% prepared by the existing semi-condensation method and the Chinese 191# universal UPR are as follows:
  • the heat resistance test was carried out by heating at a temperature of 120 ° ⁇ 1 ° C for 24 h and then at 150 ° C ⁇ 1 ° C for 3 h. The weight was measured every 3 hours.
  • the binder of DCPD modified air-drying UPR has the following effects on artificial colored quartz synthetic stone:
  • the binder in Example 1 is further substituted to further include a reactive type solvent having a weight fraction of 20%, and the reactive type solvent is styrene (St);
  • auxiliary material is added to the weight of the artificial colored quartz sand.
  • the auxiliary material is a mixture of transparent quartz sand and metal flakes.
  • the auxiliary material has a particle size of 5 to 40 mesh.
  • the accelerator is cobalt isooctylate; the amount is 0.01% by weight of the binder.
  • the organosilane coupling agent is used in an amount of 0.01% by weight of the binder.
  • the curing agent is cyclohexanone peroxide (CHP) in an amount of 0.02% by weight of the binder.
  • Curing is to uniformly mix the mixture of artificial colored quartz sand, accelerator, coupling agent and curing agent, and then press-form after vacuuming in a vacuum machine, and then solidify in a curing oven at 140 °C.
  • the above raw materials were formulated in the following parts by weight: 10 parts of natural quartz powder, 7 parts of a binder, and 50 parts of artificial colored quartz sand.
  • Artificial colored quartz sand includes artificial colored quartz sand coarse aggregate with particle size of 5-20 mesh, aggregate of artificial colored quartz sand of 20-80 mesh, artificial colored quartz sand fine aggregate of 80-200 mesh; various artificial colored quartz sand According to the following parts by weight: 20 parts of artificial colored quartz sand coarse aggregate, 40 parts of aggregate in artificial colored quartz sand, and 20 parts of artificial colored quartz sand fine aggregate.
  • the binder used in this embodiment is mainly a DCPD modified air-drying unsaturated polyester tree. Comparing the 85% DCPD modified UPR with the Chinese 191# universal UPR by semi-condensation method, the water absorption rate was reduced to 0.31%, and the volume shrinkage was reduced to 6.72%. Other parameters are as in Example 1.
  • the binder in Example 1 was replaced by a reaction type which also included a weight fraction of 35%.
  • the decomposing agent, the reactive type dissolving agent is styrene (St);
  • auxiliary material is added to the weight of the artificial colored quartz sand.
  • the auxiliary material is a mixture of transparent quartz sand and metal flakes.
  • the auxiliary material has a particle size of 5 to 40 mesh.
  • the accelerator is cobalt isooctylate; the amount is 0.5% by weight of the binder.
  • the organosilane coupling agent is used in an amount of 0.4% by weight of the binder.
  • the curing agent is tert-butyl 2-ethylhexanoate (TBPO) in an amount of 0.6% by weight of the binder.
  • TBPO tert-butyl 2-ethylhexanoate
  • Curing is to uniformly mix the mixture of artificial colored quartz sand, accelerator, coupling agent and curing agent, and then press-form after vacuuming in a vacuum machine, and then solidified in a curing oven at 145 °C.
  • the above raw materials were formulated in the following parts by weight: 30 parts of natural quartz powder, 20 parts of a binder, and 85 parts of artificial colored quartz sand.
  • Artificial colored quartz sand includes artificial colored quartz sand coarse aggregate with particle size of 5-20 mesh, aggregate of artificial colored quartz sand of 20-80 mesh, artificial colored quartz sand fine aggregate of 80-200 mesh; various artificial colored quartz sand According to the following parts by weight: 40 parts of artificial colored quartz sand coarse aggregate, 60 parts of artificial color quartz sand aggregate, 40 parts of artificial colored quartz sand fine aggregate.
  • the binder used in this embodiment is mainly a DCPD modified air-drying unsaturated polyester tree.
  • the experimental comparison of 85% DCPD modified UPR with China 191# universal UPR by semi-condensation method showed that the water absorption rate was reduced to 0.35% and the volume shrinkage rate was reduced to 6.76%.
  • Other parameters are as in Example 1.
  • the invention provides a method for producing artificial colored quartz synthetic stone from colored quartz sand, comprising the following steps:
  • the artificial colored quartz sand prepared by artificial colored quartz sand is prepared by encapsulating natural quartz sand with inorganic color paste, and drying it at a high temperature.
  • the natural quartz powder is added to the binder and stirred uniformly; the binder is a DCPD modified solvent-resistant unsaturated polyester resin.
  • the binder also includes a reactive type solvent having a weight fraction of 20% to 35%, and the reactive type solvent is styrene (St).
  • the natural quartz powder has a particle size of 325 mesh or more.
  • auxiliary materials are: one or more of transparent quartz sand, transparent cullet, luminous materials, metal sheets, and the auxiliary material has a particle size of 5 ⁇ 40 mesh.
  • the accelerator is added and stirred uniformly; the accelerator is cobalt naphthenate and cobalt isooctylate; the amount is 0.01% to 0.5% by weight of the binder.
  • the coupling agent is added and stirred uniformly; the coupling agent is an organosilane coupling agent in an amount of 0.01% to 0.4% by weight of the binder.
  • the curing agent is added and stirred uniformly; the curing agent is one of methyl ethyl ketone peroxide (MEKP), cyclohexanone peroxide (CHP), and t-butyl peroxy 2-ethylhexanoate (TBPO), and the amount is the weight of the binder. 0.02% to 0.6%.
  • MEKP methyl ethyl ketone peroxide
  • CHP cyclohexanone peroxide
  • TBPO t-butyl peroxy 2-ethylhexanoate
  • the curing is a mixture of artificial colored quartz sand, a promoter, a coupling agent, and a curing agent.
  • the curing is press-formed after vacuuming in a vacuum machine, and then solidified in a curing oven below 150 °C.
  • the above raw materials are formulated in the following parts by weight: 10 to 30 parts of natural quartz powder, 7 to 20 parts of a binder, and 50 to 85 parts of artificial colored quartz sand.
  • the artificial colored quartz sand is a spherical particle group with unequal diameters, and the particle size distribution of the particle group is complemented by pores. More specifically, the artificial colored quartz sand comprises an artificial colored quartz sand coarse aggregate having a particle diameter of 5 to 20 mesh, an aggregate of artificial colored quartz sand of 20 to 80 mesh, and an artificial colored quartz sand fine aggregate of 80 to 200 mesh;
  • the artificial colored quartz sand is proportioned according to the following parts by weight: 20-40 parts of artificial colored quartz sand coarse aggregate, 40-60 parts of aggregate in artificial colored quartz sand, and 20-40 parts of artificial colored quartz sand fine aggregate.
  • the invention provides a method for preparing artificial colored quartz synthetic stone from colored quartz sand, which uses artificial colored quartz sand as aggregate, and does not produce various pigment waste water in the processing steps of cutting, grinding and polishing after curing.
  • the invention completely eliminates the production of pigment wastewater from the source, and solves an unsolved technical problem on the road of sustainable development in the field of artificial synthetic stone manufacturing.
  • the invention further optimizes the bonding agent, and the modified bonding agent can cross-link with the dissolving agent, reduces the amount of the dissolving agent, and reduces the volatility effect of the dissolving agent, and is more in line with environmental protection requirements.
  • a step closer the particle size distribution of the particle group is complemented by pores, which can greatly improve the physical properties such as compactness, water absorption, freeze-thaw and so on.
  • the adhesive used in this embodiment is mainly DCPD modified solvent-resistant unsaturated polyester resin, and the finished product also has the characteristics of medium resistance and solvent resistance. As can be seen from the following table, its comprehensive performance has obviously exceeded that of benzene. Type unsaturated polyester resin.
  • the following table shows the mass change rate of different types of castables after immersion in different media and solvents for 90 days.
  • the invention provides a method for producing artificial colored quartz synthetic stone from colored quartz sand, comprising the following steps:
  • the natural quartz powder is added to the binder and stirred uniformly; the binder is a dicyclopentadienyl acrylate (DCPA) modified unsaturated polyester resin.
  • the binder also includes a reactive type solvent having a weight fraction of 20% to 35%, and the reactive type solvent is styrene (St).
  • the natural quartz powder has a particle size of 325 mesh or more.
  • auxiliary materials are: one or more of transparent quartz sand, transparent cullet, luminous materials, metal sheets, and the auxiliary material has a particle size of 5 ⁇ 40 mesh.
  • the accelerator is added and stirred uniformly; the accelerator is cobalt naphthenate and cobalt isooctylate; the amount is 0.01% to 0.5% by weight of the binder.
  • the coupling agent is added and stirred uniformly; the coupling agent is an organosilane coupling agent in an amount of 0.01% to 0.4% by weight of the binder.
  • the curing agent is added and stirred uniformly; the curing agent is one of methyl ethyl ketone peroxide (MEKP), cyclohexanone peroxide (CHP), and t-butyl peroxy 2-ethylhexanoate (TBPO), and the amount is the weight of the binder. 0.02% to 0.6%.
  • MEKP methyl ethyl ketone peroxide
  • CHP cyclohexanone peroxide
  • TBPO t-butyl peroxy 2-ethylhexanoate
  • the curing is a mixture of artificial colored quartz sand, a promoter, a coupling agent, and a curing agent.
  • the curing is press-formed after vacuuming in a vacuum machine, and then solidified in a curing oven below 150 °C.
  • the above raw materials are formulated in the following parts by weight: 10 to 30 parts of natural quartz powder, 7 to 20 parts of a binder, and 50 to 85 parts of artificial colored quartz sand.
  • Artificial colored quartz sand is a spherical particle group with unequal diameters.
  • the particle size distribution of a plurality of artificial artificial colored quartz F-graded particle groups is complemented by pores.
  • the artificial colored quartz sand comprises an artificial colored quartz sand coarse aggregate having a particle diameter of 5 to 20 mesh, an aggregate of artificial colored quartz sand of 20 to 80 mesh, and an artificial colored quartz sand fine aggregate of 80 to 200 mesh;
  • the artificial colored quartz sand is proportioned according to the following parts by weight: 20-40 parts of artificial colored quartz sand coarse aggregate, 40-60 parts of aggregate in artificial colored quartz sand, and 20-40 parts of artificial colored quartz sand fine aggregate.
  • the invention provides a method for preparing artificial colored quartz synthetic stone from colored quartz sand, which uses artificial colored quartz sand as aggregate, and does not produce various pigment waste water in the processing steps of cutting, grinding and polishing after curing.
  • the invention completely eliminates the production of pigment wastewater from the source, and solves an unsolved technical problem on the road of sustainable development in the field of artificial synthetic stone manufacturing.
  • the present invention further proposes the use of a dicyclopentadienyl acrylate (DCPA) modified unsaturated polyester resin as a binder in the field of synthetic quartz stone, which can be crosslinked with a solvent styrene, thereby reducing The amount of solvent used, and the volatility effect of the solvent is reduced, which is more environmentally friendly.
  • DCPA dicyclopentadienyl acrylate
  • a step closer the particle size distribution of the particle group is complemented by pores, which can greatly improve the physical properties such as compactness, water absorption, freeze-thaw and so on.
  • the adhesive used in this embodiment is mainly a dicyclopentadienyl acrylate (DCPA) modified unsaturated polyester resin.
  • DCPA dicyclopentadienyl acrylate
  • DCPA is a very useful functional monomer and it is also an important photocuring reactive diluent. Its surface energy has low viscosity, high solid content, low water absorption, small shrinkage, high hardness and good transparency. Its main performance is close to the "DCPD modified air-drying UPR" of the first embodiment. The most prominent feature is transparency, which is required by the stone industry.

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Abstract

本发明提供一种由彩色石英砂制作人造彩色石英合成石的方法，包括如下步骤：将天然石英粉加入到黏结剂中，搅拌均匀；在天然石英粉与黏结剂的混合物中加入骨料；加入促进剂、偶联剂、固化剂，搅拌均匀；真空振动压制，固化，得到人造彩色石英合成石。上述原料按照如下重量份数配比：天然石英粉10～30份、黏结剂7～20份、人工彩色石英砂50～85份。人工彩色石英砂由无机色浆料包裹天然石英砂后烘干并经高温烧结而成。本发明以彩色石英砂作为骨料，在固化后的切割、研磨、抛光等加工中不会产生各种颜料废水。本发明从源头彻底杜绝了颜料废水的产生，解决了人造合成石制造领域，可持续发展道路上一个悬而未决的技术难题。

Description

一种由彩色石英砂制作人造彩色石英合成石的方法 技术领域
本发明涉及一种人造合成石的配方和制备方法，尤其是一种人造彩色石英合成石的配方和制备方法。
背景技术
世界的人造合成石最早于20世纪60年代始于美国。1968年意大利百利通(Breton)公司推出第一条具有真空、搅拌、振动的人造石合成生产线，这是人造合成石真正具有现代意义的里程碑，它奠定了现代化人造合成石规模化生产的基础。从那时算起，人造合成石的规模化制造在全世界已经走过了50多年的发展历史。从那时起到本发明前，全世界的人造合成石制造技术和工艺一直都没有发生过比较重大的改变和显著进步。
意大利人造合成石制造技术和设备具有世界先进水平，意大利百利通公司是其杰出代表，它的人造合成石制造技术和工艺(以下统称“意大利百利通人造石技术”)是：
(碎石+树脂+色粉)常温常压混合→模具浇铸或压制成型→常温(或中低温)固化→切锯磨抛→覆膜包装→成品
意大利百利通人造石技术的特点是：
1、利用现代有机黏结剂技术，创新性地把它与石材制造很好地结合在一起，并用他们独创的连续化大生产设备制造出质量稳定、可靠、性能好、科技含量高的高品质人造合成石产品。
2、从技术工艺角度看，石材有机黏结剂在常压、常温下就可以固化，并不需要加热固化，也不需要能源消耗。但是为了提高规模化生产的速度和效益，规模企业一般都采用低温加热的方式使产品快速固化，缩短生产周期。由于低温加热温度低，能耗也就不高，但所带来的经济效益却很可观。
3、由于工艺简单，设备复杂程度也低，投资也就相对不大，更 有利于自动化高效生产。
“意大利百利通人造石技术”处于世界领先水平。到2008年末，它在全世界已经卖出了180条以上的百利通人造合成石设备生产线。
4、意大利百利通人造石技术方案中的着色方法是：把无机或有机颜料分散、溶解在树脂里，靠树脂来黏结天然的石粒、石砂并包裹着色。由于色料与树脂的分散、溶解与兼容性问题，树脂硬度的相对较软等客观因素和技术难度，造成了人造合成石的光泽度很难提高、色彩单一、每批与每批颜色一致性差、成品合格率低等问题。人造合成石的这方面性能，在本发明前还是无法与天然花岗石，大理石等石材产品相比。
意大利百利通公司生产的百利通牌人造石英石产品所能达到的性能参数，及与天然石材性能的对比是：
Figure PCTCN2015073295-appb-000001
Figure PCTCN2015073295-appb-000002
通过对50多年的生产实践和经验的总结，我们发现“意大利百利通人造石技术”还存在着两个明显的不足和重大缺陷：
一是，生产的环境和废料处理的问题：
(1)目前世界上制造人造合成石所使用的黏结剂大都为邻苯型和间苯型不饱和聚脂树脂(UPR)。其由不饱和聚脂溶解在苯乙烯(St)里制成不饱和聚脂树脂。St在树脂中主要起稀释和交联作用，正常使用量一般在35％～45％。虽然不饱和聚脂树脂固化后对环境和人体不会带来破坏和健康危害，但是在常温下St的蒸汽压高，易挥发，有刺激性气味，它带来的作业环境会较差，不符合环保要求。
(2)固化后的彩色人造合成石毛坯料一般都需要经过切割、研磨、抛光等加工工序。加工中会产生各种颜料废水(主要成份是无机色料)和比较多的细砂和石粉(约占产品总重量的3％左右)。细砂和石粉比较好处理：量小的话，一般都是先过滤压干后再无害化填埋；量大的话，一般都把它制作成各种形状的建筑砖，废物回收再利用。但各种混合颜料废水就比较难处理了，虽然很多企业也采取了吸附、沉淀、过滤和循环处理等工艺技术进行处理，但也只能是减小污染，勉强达到环保要求，还未从根本上彻底解决该环保问题。它已成为人造合成石制造企业可持续发展道路上一个非常急迫，需要科学、有效地解决的重大环保问题。
二是，按“意大利百利通人造石技术”生产出的人造合成石产品，其在颜色、光泽、花纹、纹理和质感等方面还无法达到目前优质天然大理石、花岗石等石材所能达到的性能水平。作为建筑装饰材料，外观的鲜艳靓丽与美感是一个非常直观和重要的评判指标，它会直接影 响人们判断它是否高端，是否高档等，这直接影响其销售价格的高低！以上几点主要体现在以下三个方面的问题：
1、颜色：色泽的鲜艳、纯正、深邃及层次感方面还无法表现或表现不足；
2、纹理和质感：图案纹理的自然、逼真、质感及多样性方面还无法表现或表现不足；
3、光泽度：光泽的靓丽、生动性方面还无法提高或效果不佳。
发明内容
本发明的发明目的在提出一种由彩色石英砂制作人造彩色石英合成石的方法，解决上述现有技术问题中的一个或者多个。
根据本发明的一个方面，提供一种由彩色石英砂制作人造彩色石英合成石的方法，包括如下步骤：
准备人工彩色石英砂，人工彩色石英砂是由无机色浆料包裹天然石英砂后烘干并经高温烧结而成。
将天然石英粉加入到黏结剂中，搅拌均匀；
在天然石英粉与黏结剂的混合物中加入人工彩色石英砂，搅拌均匀；
加入促进剂，搅拌均匀；
加入偶联剂，搅拌均匀；
加入固化剂，搅拌均匀；
于真空环境下均匀布料后压制成形，再经固化，得到人造彩色石英合成石；
上述原料按照如下重量份数配比：天然石英粉10～30份、黏结剂7～20份、人工彩色石英砂50～85份。
本发明提供了一种由彩色石英砂制作人造彩色石英合成石的方法，以彩色石英砂作为骨料，在固化后的切割、研磨、抛光等加工工序中，不会产生各种颜料废水，本发明从源头彻底杜绝了颜料废水的产生，解决了人造合成石制造领域可持续发展道路上一个悬而未决的 技术难题。
在一些实施方式中，黏结剂为经双环戊二烯(简称DCPD)或其衍生物改性的不饱和聚酯树脂(简称UPR)。
在人造合成石领域，目前国内外普遍使用的黏结剂为：邻苯型和间苯型不饱和聚脂树脂(UPR)，通用UPR中苯乙烯(简称St)含量一般为35％～45％，它由不饱和聚脂溶解在St里制得，St在其中主要起稀释和交联作用。虽然UPR固化后对环境和人体的健康无危害。但是在常温下，St的蒸汽压较高，易挥发，有刺激性气味，它带来的作业环境会较差，不符合环保要求。
本发明进一步优化了黏结剂，优化方法是：通过DCPD及其衍生物与UPR的结合，减少了St的用量，其机理是：
(a)由于DCPD加成法中的链中止反应可以降低UPR的分子重量，降低了粘度；
(b)、用DCPD对聚合物链的端基进行改性，使聚合物链具有非极性C-H末端，增强了树脂对St中的相溶性。
这两方面作用都降低了St的所需量，因而达到了降低St重量分数的目的。
经DCPD及其衍生物改性的不饱和聚酯树脂相对于其他改性树脂的优点体现在以下方面：
经DCPD及其衍生物改性后的UPR综合性能好，特别能满足石材行业所需的一些重要指标：如收缩率低(可从改性前的9％左右降到3％左右)；耐水性优良(可在水中长时间浸泡)；耐热性高(200℃以下热稳定性很强)、耐紫外光(可在阳光下长时间爆晒)、耐化学腐蚀好、低挥发性、制品机械性能高(如弯曲强度等)。
施工工艺性好、存储期长、固化时间短、黏接强度高、光泽度高、成本较低等特点。
DCPD和St的接枝共聚具有良好的亲和性、相容性和互容性。由于DCPD分子中含有多个不饱和双键，化学性质活泼。DCPD是端基封闭剂，DCPD加成在不饱和聚脂分子链两端，当树脂固化时，在 引发剂作用下，固化反应放热到一定温度时，DCPD封端中的五元环上的不饱和双键打开成为交联点，参与交联反应，增加了交联密度，从而改变了树脂的性能
因此，用DCPD改性后的UPR，St的挥发性和挥发量大幅度减少。据实际测量:其挥发量可以减少50％以上(一种粗略算法：St使用量每降低1％，在固化阶段St挥发将降低5％)。
在一些实施方式中，黏结剂为DCPD改性气干性不饱和聚酯树脂、DCPD改性耐溶剂型不饱和聚酯树脂、丙烯酸双环戊二烯酯(DCPA)改性不饱和聚酯树脂。
在一些实施方式中，天然石英粉的粒径在325目以上，人工彩色石英砂为形状不等径的球形粒子群，粒子群的粒度分布呈孔隙互补的级配。
粒子群的粒度分布呈孔隙互补的级配，可以大大提高制品的密实度、吸水率、冻融性等物理性能。
在一些实施方式中，人工彩色石英砂包括粒径在5～20目的人工彩色石英砂粗骨料、20～80目的人工彩色石英砂中骨料、80～200目的人工彩色石英砂细骨料；上述多种人工彩色石英砂按照如下重量份数配比：人工彩色石英砂粗骨料20～40份，人工彩色石英砂中骨料40～60份，人工彩色石英砂细骨料20～40份。
粒子群的粒度分布呈孔隙互补的级配，可以大大提高制品的密实度、吸水率、冻融性等物理性能。
在一些实施方式中，在加入固化剂前还加入人工彩色石英砂重量的30％以下的辅助性材料，辅助性材料为：透明石英砂、透明碎玻璃、夜光材料、金属片中的一种或者多种，辅助性材料的粒径在5～40目。
加入合适的辅助性材料可以提高产品的视觉美感，使产品在阳光下有瑰丽、绚烂的视觉感受。
在一些实施方式中，固化剂为过氧化甲乙酮(MEKP)、过氧化环乙酮(CHP)、过氧化2-乙基己酸叔丁酯(TBPO)；偶联剂为有机硅烷偶联剂，促进剂为环烷酸钴、异辛酸钴；
固化剂的重量为黏结剂重量的0.02％～0.6％；偶联剂的重量为黏结剂重量的0.01％～0.4％；促进剂的重量为黏结剂重量的0.01％～0.5％。
有机硅烷偶联剂的通式为RSiX3，可选的品种有：中国科学院的KH-507、KH-1714；日本信越化学的KE420、KE340、KE109等。
在一些实施方式中，所述固化是将已加入人工彩色石英砂、促进剂、偶联剂、固化剂的混合物经匀料设备均匀布料，并在真空机抽真空后压制成形，然后置于150℃以下的固化炉中固化。
在一些实施方式中，黏结剂中还包括重量分数为20％～35％的反应型溶解剂，反应型溶解剂为苯乙烯(St)。
应当指出，本发明采用的彩色石英砂的理化性能指标应当符合GB/T 14684-2011《建设用砂》；GB/T 1768《色漆和清漆耐磨性的测试旋转橡胶砂轮法》；JC/T 753-2001《硅质玻璃原料化学分析方法》；JC/T 1071-2008《沥青瓦用彩砂》的标准。目前世界和中国都还没有有关《彩色石英砂》的任何标准。本发明所选用的石英彩砂，在理论上只要能满足特定的各项理化指标，不论是人工彩砂还是天然彩砂都是可以选用的。
具体实施方式
实施例1：
本发明提供了一种由彩色石英砂制作人造彩色石英合成石的方法，包括如下步骤：
准备人工彩色石英砂，人工彩色石英砂是由无机色浆料包裹天然石英砂后烘干并经高温烧结而成。
将天然石英粉加入到黏结剂中，搅拌均匀；黏结剂为DCPD改性气干性不饱和聚酯树脂。黏结剂中还包括重量分数为30％的反应型溶解剂，反应型溶解剂为苯乙烯(St)。
在天然石英粉与黏结剂的混合物中加入人工彩色石英砂，搅拌均匀；天然石英粉的粒径在325目以上。
加入促进剂，搅拌均匀；促进剂为环烷酸钴；用量为黏结剂重量的0.2％。
加入偶联剂，搅拌均匀；偶联剂为有机硅烷偶联剂，用量为黏结剂重量的0.2％。
加入固化剂，搅拌均匀；固化剂为过氧化甲乙酮(MEKP)，用量为黏结剂重量的0.3％。
于真空环境下均匀布料后压制成形，再经固化，得到人造彩色石英合成石；更为具体，固化是将已加入人工彩色石英砂、促进剂、偶联剂、固化剂的混合物经匀料设备均匀布料后，在真空机抽真空后压制成形，然后置于150℃的固化炉中固化。
上述原料按照如下重量份数配比：天然石英粉20份、黏结剂15份、人工彩色石英砂65份。
人工彩色石英砂为形状不等径的球形粒子群，粒子群的粒度分布呈孔隙互补的级配。更具体的，人工彩色石英砂包括粒径在5～20目的人工彩色石英砂粗骨料、20～80目的人工彩色石英砂中骨料、80～200目的人工彩色石英砂细骨料；上述多种人工彩色石英砂按照如下重量份数配比：人工彩色石英砂粗骨料30份，人工彩色石英砂中骨料50份，人工彩色石英砂细骨料30份。
本发明提供了一种由彩色石英砂制作人造彩色石英合成石的方法，以彩色石英砂作为骨料，在固化后的切割、研磨、抛光等加工工序中，不会产生各种颜料废水，本发明从源头彻底杜绝了颜料废水的产生，解决了人造合成石制造领域可持续发展道路上一个悬而未决的技术难题。
此外，本发明进一步优化了黏结剂，经过改性后的黏结剂可与溶解剂进行交联反应，降低了溶解剂的使用量，并且降低了溶解剂的挥发性效应，更加符合环保要求。
更近一步：粒子群的粒度分布呈孔隙互补的级配，可以大大提高制品的密实度、吸水率、冻融性等物理性能。
以本实施例制作的人造彩色石英合成石具备如下物理强度：
项目 数值 标准
抗压强度/MPa 278 德国DIN 52105测试标准
抗弯强度/MPa 178 意大利UNI 10443测试标准
冲击试验/J 41.6 意大利UNI 10442测试标准
吸水率/％ 0.01 意大利DIN 10444测试标准
冻融25次后抗压强度/MPa 258 德国DIN 52104测试标准
耐磨损/mm3 160 意大利UNI 10532测试标准
表观密度/(g/cm3) 2.59 意大利DIN 10444测试标准
本实施例采用的黏结剂主要为DCPD改性气干性不饱和聚酯树脂。用现有的半缩聚法制得含量为85％的DCPD改性气干性UPR与中国191#通用UPR进行实验对比数据如下：
表1 DCPD改性树脂与191*树脂化学物理及力学性能比较*
Figure PCTCN2015073295-appb-000003
*191*树脂系部优产品。两种树脂在同等条件下测定。
表2 DCPD改性树脂与191*树脂浇铸体耐热试验(重量损失％)*
Figure PCTCN2015073295-appb-000004
*耐热试验是在120°±1℃的温度场下加热24h，后又在150℃±1℃的温度下加热3h。每间隔3h测定一次重量。
算出重量损失率。加热18h后191*试块出现裂缝，150℃下3h试块炭化龟裂，DCPD型试块仅颜色变得稍深。
表3 DCPD型树脂气干性表征指标
Figure PCTCN2015073295-appb-000005
*DCPD型树脂不家石蜡**191*树脂家有石蜡
表4树脂浇铸体耐化学腐蚀性能(重量变化％)*
Figure PCTCN2015073295-appb-000006
*“-”表示减重
通过以上数据得出DCPD改性气干性UPR的黏结剂对人造彩色石英合成石还具有以下影响：
吸水率低(见表1，从约0.38％降到0.24％)；体积收缩率减少(见表1，从7.98％降到6.42％)；力学强度提高(见表1中的拉伸强度、弯曲强度、压缩强度对比)；硬度增大(见表1，从36提高到44)；气干性好(见表3)；耐热性良好(见表2)；耐腐蚀性强(见表4)等。
实施例2：
将实施例1中黏结剂替换为还包括重量分数为20％的反应型溶解剂，反应型溶解剂为苯乙烯(St)；
另加入人工彩色石英砂重量的30％的辅助性材料，辅助性材料为透明石英砂和金属片的混合物，辅助性材料的粒径在5～40目。
促进剂为异辛酸钴；用量为黏结剂重量的0.01％。
有机硅烷偶联剂，用量为黏结剂重量的0.01％。
固化剂为过氧化环乙酮(CHP)，其用量为黏结剂重量的0.02％。
固化是将已加入人工彩色石英砂、促进剂、偶联剂、固化剂的混合物经匀料设备均匀布料后，在真空机抽真空后压制成形，然后置于140℃的固化炉中固化。
上述原料按照如下重量份数配比：天然石英粉10份、黏结剂7份、人工彩色石英砂50份。人工彩色石英砂包括粒径在5～20目的人工彩色石英砂粗骨料、20～80目的人工彩色石英砂中骨料、80～200目的人工彩色石英砂细骨料；多种人工彩色石英砂按照如下重量份数配比：人工彩色石英砂粗骨料20份，人工彩色石英砂中骨料40份，人工彩色石英砂细骨料20份。
其他步骤与参量与实施例1相同，此处不再赘述。
以本实施例制作的人造彩色石英合成石具备如下物理强度：
项目 数值 标准
抗压强度/MPa 235 德国DIN 52105测试标准
抗弯强度/MPa 122 意大利UNI 10443测试标准
冲击试验/J 9.75 意大利UNI 10442测试标准
吸水率/％ 0.025 意大利DIN 10444测试标准
冻融25次后抗压强度/MPa 216 德国DIN 52104测试标准
耐磨损/mm3 142 意大利UNI 10532测试标准
表观密度/(g/cm3) 2.48 意大利DIN 10444测试标准
本实施例采用的黏结剂主要为DCPD改性气干性不饱和聚酯树。用半缩聚法制得85％含量DCPD改性UPR与中国191#通用UPR进行实验对比可发现，吸水率降低至0.31％，体积收缩率减少至6.72％。其他参数如实施例1。
实施例3：
将实施例1中黏结剂替换为还包括重量分数为35％的反应型溶 解剂，反应型溶解剂为苯乙烯(St)；
另加入人工彩色石英砂重量的30％的辅助性材料，辅助性材料为透明石英砂和金属片的混合物，辅助性材料的粒径在5～40目。
促进剂为异辛酸钴；用量为黏结剂重量的0.5％。
有机硅烷偶联剂，用量为黏结剂重量的0.4％。
固化剂为过氧化2-乙基己酸叔丁酯(TBPO)，其用量为黏结剂重量的0.6％。
固化是将已加入人工彩色石英砂、促进剂、偶联剂、固化剂的混合物经匀料设备均匀布料后，在真空机抽真空后压制成形，然后置于145℃的固化炉中固化。
上述原料按照如下重量份数配比：天然石英粉30份、黏结剂20份、人工彩色石英砂85份。人工彩色石英砂包括粒径在5～20目的人工彩色石英砂粗骨料、20～80目的人工彩色石英砂中骨料、80～200目的人工彩色石英砂细骨料；多种人工彩色石英砂按照如下重量份数配比：人工彩色石英砂粗骨料40份，人工彩色石英砂中骨料60份，人工彩色石英砂细骨料40份。
其他步骤与参量与实施例1相同，此处不再赘述。
以本实施例制作的人造彩色石英合成石具备如下物理强度：
项目 数值 标准
抗压强度/MPa 242 德国DIN 52105测试标准
抗弯强度/MPa 99 意大利UNI 10443测试标准
冲击试验/J 24.52 意大利UNI 10442测试标准
吸水率/％ 0.03 意大利DIN 10444测试标准
冻融25次后抗压强度/MPa 225 德国DIN 52104测试标准
耐磨损/mm3 110 意大利UNI 10532测试标准
表观密度/(g/cm3) 2.51 意大利DIN 10444测试标准
本实施例采用的黏结剂主要为DCPD改性气干性不饱和聚酯树。用半缩聚法制得85％含量DCPD改性UPR与中国191#通用UPR进行实验对比可发现，吸水率降低至0.35％，体积收缩率减少至6.76％。其他参数如实施例1。
实施例4：
本发明提供了一种由彩色石英砂制作人造彩色石英合成石的方法，包括如下步骤：
准备人工彩色石英砂，的人工彩色石英砂是由无机色浆料包裹天然石英砂后烘干并经高温烧结而成。
将天然石英粉加入到黏结剂中，搅拌均匀；黏结剂为DCPD改性耐溶剂型不饱和聚酯树脂。黏结剂中还包括重量分数为20％～35％的反应型溶解剂，反应型溶解剂为苯乙烯(St)。
在天然石英粉与黏结剂的混合物中加入人工彩色石英砂，搅拌均匀；天然石英粉的粒径在325目以上。
加入人工彩色石英砂重量的30％以下的辅助性材料，辅助性材料为：透明石英砂、透明碎玻璃、夜光材料、金属片中的一种或者多种，辅助性材料的粒径在5～40目。
加入促进剂，搅拌均匀；促进剂为环烷酸钴、异辛酸钴；用量为黏结剂重量的0.01％～0.5％。
加入偶联剂，搅拌均匀；偶联剂为有机硅烷偶联剂，用量为黏结剂重量的0.01％～0.4％。
加入固化剂，搅拌均匀；固化剂为过氧化甲乙酮(MEKP)、过氧化环乙酮(CHP)、过氧化2-乙基己酸叔丁酯(TBPO)中的一种，用量为黏结剂重量的0.02％～0.6％。
于真空环境下均匀布料后压制成形，再经固化，得到人造彩色石英合成石；更为具体，固化是将已加入人工彩色石英砂、促进剂、偶联剂、固化剂的混合物经匀料设备均匀布料后，在真空机抽真空后压制成形，然后置于150℃以下的固化炉中固化。
上述原料按照如下重量份数配比：天然石英粉10～30份、黏结剂7～20份、人工彩色石英砂50～85份。
人工彩色石英砂为形状不等径的球形粒子群，粒子群的粒度分布呈孔隙互补的级配。更具体的，人工彩色石英砂包括粒径在5～20目的人工彩色石英砂粗骨料、20～80目的人工彩色石英砂中骨料、80～200目的人工彩色石英砂细骨料；上述多种人工彩色石英砂按照如下重量份数配比：人工彩色石英砂粗骨料20～40份，人工彩色石英砂中骨料40～60份，人工彩色石英砂细骨料20～40份。
本发明提供了一种由彩色石英砂制作人造彩色石英合成石的方法，以人工彩色石英砂作为骨料，在固化后的切割、研磨、抛光等加工工序中，不会产生各种颜料废水，本发明从源头彻底杜绝了颜料废水的产生，解决了人造合成石制造领域可持续发展道路上一个悬而未决的技术难题。
此外，本发明进一步优化了黏结剂，经过改性后的黏结剂可与溶解剂进行交联反应，降低了溶解剂的使用量，并且降低了溶解剂的挥发性效应，更加符合环保要求。
更近一步：粒子群的粒度分布呈孔隙互补的级配，可以大大提高制品的密实度、吸水率、冻融性等物理性能。
以本实施例制作的人造彩色石英合成石具备如下物理强度：
项目 数值 标准
抗压强度/MPa 203～258 德国DIN 52105测试标准
抗弯强度/MPa 72～118 意大利UNI 10443测试标准
冲击试验/J 8.9～28.87 意大利UNI 10442测试标准
吸水率/％ 0.05～0.01 意大利DIN 10444测试标准
冻融25次后抗压强度/MPa 198～243 德国DIN 52104测试标准
耐磨损/mm3 126～155 意大利UNI 10532测试标准
表观密度/(g/cm3) 2.45～2.58 意大利DIN 10444测试标准
本实施例采用的黏结剂主要为DCPD改性耐溶剂型不饱和聚酯树脂，其成品还具有：耐介质性、耐溶剂性等特点，由下表可见，其综合性能已明显超过了间苯型不饱和聚酯树脂。
下表为不同类型浇注体在不同介质、溶剂中浸泡90天后的质量变化率。
类型 水中 5％HNO3溶液 5％NaOH溶液
邻苯型 0.832％ 1.087％ 6.922％
间苯型 0.374％ 1.026％ 0.66l％
DCPD型 0.252％ 0.308％ 0.172％
实施例5：
本发明提供了一种由彩色石英砂制作人造彩色石英合成石的方法，包括如下步骤：
准备人工彩色石英砂，人工彩色石英砂是由无机色浆料包裹天然石英砂后烘干并经高温烧结而成。
将天然石英粉加入到黏结剂中，搅拌均匀；黏结剂为丙烯酸双环戊二烯酯(DCPA)改性不饱和聚酯树脂。黏结剂中还包括重量分数为20％～35％的反应型溶解剂，反应型溶解剂为苯乙烯(St)。
在天然石英粉与黏结剂的混合物中加入人工彩色石英砂，搅拌均匀；天然石英粉的粒径在325目以上。
加入人工彩色石英砂重量的30％以下的辅助性材料，辅助性材料为：透明石英砂、透明碎玻璃、夜光材料、金属片中的一种或者多种，辅助性材料的粒径在5～40目。
加入促进剂，搅拌均匀；促进剂为环烷酸钴、异辛酸钴；用量为黏结剂重量的0.01％～0.5％。
加入偶联剂，搅拌均匀；偶联剂为有机硅烷偶联剂，用量为黏结剂重量的0.01％～0.4％。
加入固化剂，搅拌均匀；固化剂为过氧化甲乙酮(MEKP)、过氧化环乙酮(CHP)、过氧化2-乙基己酸叔丁酯(TBPO)中的一种，用量为黏结剂重量的0.02％～0.6％。
于真空环境下均匀布料后压制成形，再经固化，得到人造彩色石英合成石；更为具体，固化是将已加入人工彩色石英砂、促进剂、偶联剂、固化剂的混合物经匀料设备均匀布料后，在真空机抽真空后压制成形，然后置于150℃以下的固化炉中固化。
上述原料按照如下重量份数配比：天然石英粉10～30份、黏结剂7～20份、人工彩色石英砂50～85份。
人工彩色石英砂为形状不等径的球形粒子群，多种人工人工彩色石英F梯度化的粒子群的粒度分布呈孔隙互补的级配。更具体的，人工彩色石英砂包括粒径在5～20目的人工彩色石英砂粗骨料、20～80目的人工彩色石英砂中骨料、80～200目的人工彩色石英砂细骨料；上述多种人工彩色石英砂按照如下重量份数配比：人工彩色石英砂粗骨料20～40份，人工彩色石英砂中骨料40～60份，人工彩色石英砂细骨料20～40份。
本发明提供了一种由彩色石英砂制作人造彩色石英合成石的方法，以人工彩色石英砂作为骨料，在固化后的切割、研磨、抛光等加工工序中，不会产生各种颜料废水，本发明从源头彻底杜绝了颜料废水的产生，解决了人造合成石制造领域可持续发展道路上一个悬而未决的技术难题。
此外，本发明进一步提出了丙烯酸双环戊二烯酯(DCPA)改性不饱和聚酯树脂作为黏结剂在人造合成石英石领域中的应用，其可与溶解剂苯乙烯进行交联反应，降低了溶解剂的使用量，并且降低了溶解剂的挥发性效应，更加符合环保要求。
更近一步：粒子群的粒度分布呈孔隙互补的级配，可以大大提高制品的密实度、吸水率、冻融性等物理性能。
以本实施例制作的人造彩色石英合成石具备如下物理强度：
项目 数值 标准
抗压强度/MPa 218～258 德国DIN 52105测试标准
抗弯强度/MPa 116～132 意大利UNI 10443测试标准
冲击试验/J 8.9～38.87 意大利UNI 10442测试标准
吸水率/％ 0.02～0.01 意大利DIN 10444测试标准
冻融25次后抗压强度/MPa 215～248 德国DIN 52104测试标准
耐磨损/mm3 120～145 意大利UNI 10532测试标准
表观密度/(g/cm3) 2.46～2.59 意大利DIN 10444测试标准
本实施例采用的黏结剂主要为丙烯酸双环戊二烯酯(DCPA)改性不饱和聚酯树脂。
DCPA是一种很有特点的功能单体，它也是很重要的光固化活性稀释剂。它表面能低黏度小、固含量高、低吸水率、收缩率小、硬度大、透明度性好。其主要性能除与实施例1的“DCPD改性气干性UPR”接近外，最突出的特质是透明性好，这一特质是石材行业所需要的。
以上所述仅是本发明的优选方式，应当指出，对于本领域技术人员来说，在不脱离本发明创造构思的前提下，还可以做出若干相似的变形和改进，这些也应视为本发明的保护范围之内。

Claims (9)

  1. 一种由彩色石英砂制作人造彩色石英合成石的方法，其特征在于，包括如下步骤：
    准备人工彩色石英砂，所述人工彩色石英砂是由无机色浆料包裹天然石英砂后烘干并经高温烧结而成；
    将天然石英粉加入到黏结剂中，搅拌均匀；
    在天然石英粉与黏结剂的混合物中加入所述人工彩色石英砂，搅拌均匀；
    加入促进剂，搅拌均匀；
    加入偶联剂，搅拌均匀；
    加入固化剂，搅拌均匀；
    于真空环境下均匀布料后压制成形，再经固化，得到人造彩色石英合成石；
    上述原料按照如下重量份数配比：天然石英粉10～30份、黏结剂7～20份、人工彩色石英砂50～85份。
  2. 根据权利要求1所述的一种由彩色石英砂制作人造彩色石英合成石的方法，其特征在于，所述黏结剂为经双环戊二烯或其衍生物改性的不饱和聚酯树脂。
  3. 根据权利要求2所述的一种由彩色石英砂制作人造彩色石英合成石的方法，其特征在于，所述黏结剂为双环戊二烯改性气干性不饱和聚酯树脂、双环戊二烯改性耐溶剂型不饱和聚酯树脂、丙烯酸双环戊二烯酯改性不饱和聚酯树脂。
  4. 根据权利要求1所述的一种由彩色石英砂制作人造彩色石英合成石的方法，其特征在于，所述天然石英粉的粒径在325目以上，所述人工彩色石英砂为形状不等径的球形粒子群，所述粒子群的粒度分布呈孔隙互补的级配。
  5. 根据权利要求4所述的一种由彩色石英砂制作人造彩色石英合成石的方法，其特征在于，所述人工彩色石英砂包括粒径在5～20目的人工彩色石英砂粗骨料、20～80目的人工彩色石英砂中骨料、80～200目的人工彩色石英砂细骨料；
    上述多种人工彩色石英砂按照如下重量份数配比：所述人工彩色石英砂粗骨料20～40份，所述人工彩色石英砂中骨料40～60份，所述人工彩色石英砂细骨料20～40份。
  6. 根据权利要求1所述的一种由彩色石英砂制作人造彩色石英合成石的方法，其特征在于，在加入固化剂前还加入所述人工彩色石英砂重量的30％以下的辅助性材料，所述辅助性材料为：透明石英砂、透明碎玻璃、夜光材料、金属片中的一种或者多种，所述辅助性材料的粒径在5～40目。
  7. 根据权利要求1所述的一种由彩色石英砂制作人造彩色石英合成石的方法，其特征在于：所述固化剂为过氧化甲乙酮、过氧化环乙酮、过氧化2-乙基己酸叔丁酯；所述偶联剂为有机硅烷偶联剂，所述促进剂为环烷酸钴、异辛酸钴；
    所述固化剂的重量为所述黏结剂重量的0.02％～0.6％；
    所述偶联剂的重量为所述黏结剂重量的0.01％～0.4％；
    所述促进剂的重量为所述黏结剂重量的0.01％～0.5％。
  8. 根据权利要求1所述的一种由彩色石英砂制作人造彩色石英合成石的方法，其特征在于，所述固化是将已加入人工彩色石英砂、促进剂、偶联剂、固化剂的混合物经匀料设备均匀布料，并在真空机抽真空后压制成形，然后置于150℃以下的固化炉中固化。
  9. 根据权利要求2所述的一种由彩色石英砂制作人造彩色石英 合成石的方法，其特征在于，所述黏结剂中还包括重量分数为20％～35％的反应型溶解剂，所述反应型溶解剂为苯乙烯。
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CN106186804A (zh) * 2016-06-30 2016-12-07 禹州市远大塑料电器有限责任公司 一种防腐的人造石英石板材及其制备工艺
CN106186822A (zh) * 2016-06-30 2016-12-07 禹州市远大塑料电器有限责任公司 一种耐磨石英石板材及其制备工艺
CN108117301A (zh) * 2016-11-29 2018-06-05 安徽省安美利特环保材料科技有限公司 一种免烧结的填充式真空石制备工艺
CN108117303A (zh) * 2016-11-29 2018-06-05 安徽省安美利特环保材料科技有限公司 一种免烧结的填充式真空石
CN107628770A (zh) * 2017-08-28 2018-01-26 北京宝莲纳新材料技术有限公司 高效无缝石坪复合软料、石坪硬质板材及其制作工艺
CN114379173B (zh) * 2021-12-28 2022-08-12 广东中旗新材料股份有限公司 一种多层人造石英石、制备方法及制备设备

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1063273A (zh) * 1992-03-12 1992-08-05 魏立文 彩色石英砂及其表面彩釉工艺
CN102180609A (zh) * 2011-01-28 2011-09-14 牛智勇 一种玻化彩砂的制备工艺
CN102408201A (zh) * 2011-08-12 2012-04-11 新云石业（云浮）有限公司 保健人造石英石板材原料、人造石英石板材及其制备方法
CN102627429A (zh) * 2012-03-27 2012-08-08 武汉石尚高新建材有限公司 人造石英石板材原料、人造石英石板材及其制备方法
CN102659348A (zh) * 2012-04-16 2012-09-12 武汉石尚高新建材有限公司 人造石英石板材原料和利用其制备人造石英石的方法
CN104230214A (zh) * 2014-09-17 2014-12-24 常州明清新材料技术有限公司 一种由彩色石英砂制作人造彩色石英合成石的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1986474A (zh) * 2005-12-19 2007-06-27 黄艳 一种彩色装饰石英砂的制造方法
CN102229189B (zh) * 2011-06-21 2013-03-20 云浮市新富云岗石有限公司 一种方料型人造石英石板材及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1063273A (zh) * 1992-03-12 1992-08-05 魏立文 彩色石英砂及其表面彩釉工艺
CN102180609A (zh) * 2011-01-28 2011-09-14 牛智勇 一种玻化彩砂的制备工艺
CN102408201A (zh) * 2011-08-12 2012-04-11 新云石业（云浮）有限公司 保健人造石英石板材原料、人造石英石板材及其制备方法
CN102627429A (zh) * 2012-03-27 2012-08-08 武汉石尚高新建材有限公司 人造石英石板材原料、人造石英石板材及其制备方法
CN102659348A (zh) * 2012-04-16 2012-09-12 武汉石尚高新建材有限公司 人造石英石板材原料和利用其制备人造石英石的方法
CN104230214A (zh) * 2014-09-17 2014-12-24 常州明清新材料技术有限公司 一种由彩色石英砂制作人造彩色石英合成石的方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115159894A (zh) * 2022-07-06 2022-10-11 福建磐珉新材有限公司 一种具有流纹状花纹的人造石英石板材
CN115140979A (zh) * 2022-07-18 2022-10-04 三能集成房屋股份有限公司 一种改性彩色uhpc混合料、装饰板及其制备方法
CN115140979B (zh) * 2022-07-18 2024-03-19 三能集成房屋股份有限公司 一种改性彩色uhpc混合料、装饰板及其制备方法
CN116947421A (zh) * 2023-07-28 2023-10-27 江西省建材科研设计院有限公司 基于集料级配模型设计的超疏水人造石英板及其制备方法

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