WO2011150637A1 - 一种彩色硅砂及其制备方法 - Google Patents

一种彩色硅砂及其制备方法 Download PDF

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Publication number
WO2011150637A1
WO2011150637A1 PCT/CN2010/079430 CN2010079430W WO2011150637A1 WO 2011150637 A1 WO2011150637 A1 WO 2011150637A1 CN 2010079430 W CN2010079430 W CN 2010079430W WO 2011150637 A1 WO2011150637 A1 WO 2011150637A1
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Prior art keywords
silica sand
colored
weight
resin
sand according
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PCT/CN2010/079430
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English (en)
French (fr)
Inventor
秦升益
王振邦
胡文星
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北京仁创科技集团有限公司
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Priority claimed from CN 201010195458 external-priority patent/CN102260054A/zh
Priority claimed from CN 201010195457 external-priority patent/CN102260053A/zh
Application filed by 北京仁创科技集团有限公司 filed Critical 北京仁创科技集团有限公司
Publication of WO2011150637A1 publication Critical patent/WO2011150637A1/zh

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28Compounds of silicon
    • C09C1/30Silicic acid
    • C09C1/3072Treatment with macro-molecular organic compounds

Definitions

  • the invention relates to a colored silica sand and a preparation method thereof. Background technique
  • Silica sand also known as quartz sand, is a hard, wear-resistant, chemically stable silicate mineral with a particle size of 0.020mm-3.350mm. Its main mineral component is silica.
  • the color of silica sand is milky white or colorless. Translucent, with a hardness of 7. and a relative density of 2.65, the chemical, thermal and mechanical properties of silica sand are clearly anisotropic. Due to the unique physical and chemical properties of silica sand, it is widely used in many fields such as glass, foundry, ceramics, metallurgy, construction, and chemical industry.
  • Natural silica sand is rich in resources, such as aeolian sand, river sand and sea sand, etc., and is inexpensive, and is often used as a main raw material for some water-permeable materials such as sand-permeable bricks and permeable pavements in the field of building materials, but these The natural silica sand has a single color and cannot meet the needs of modern colorful building materials when it is applied as a building material. Further, when the silica sand is dyed by an ordinary method, it is difficult to color the silica sand due to the special properties of the silica sand, and it is more difficult to obtain a colored silica sand having a long-term color stability after coloring. Summary of the invention
  • the object of the present invention is to overcome the problems of single color, difficulty in coloring, and poor long-term color stability after coloring in the prior art, and to provide a colored silica sand which is easy to color and has good long-term color stability after coloring and a preparation method thereof.
  • the present invention provides a colored silica sand comprising a silica sand substrate and a colored resin layer coated on the surface of the silica sand substrate, the colored resin layer being cured by a mixture containing the pigment agent, Resin and curing agent.
  • the invention also provides a preparation method of the above colored silica sand, wherein the method comprises: The silica sand substrate is uniformly mixed with the resin at 100 to 200 ° C, and then the mixture of the silica sand substrate and the resin is brought into contact with the pigment agent and the curing agent to form a colored resin layer on the surface of the silica sand substrate.
  • the present invention can achieve polychromatic coloration of silica sand by coating a surface of a silica sand substrate with a colored resin layer, and the color stability of the obtained colored silica sand can be maintained due to the good physical and chemical properties of the resin.
  • the method for preparing colored silica sand of the present invention is formed by uniformly mixing a silica sand substrate with a resin at 100-200 ° C, and then contacting a mixture of the silica sand substrate and the resin with a pigment agent and a curing agent to form a surface of the silica sand substrate.
  • the color resin layer enables the silica sand substrate to be more closely bonded to the colored resin layer, thereby avoiding the problem of color shedding and ensuring the long-term stability of the pigment on the surface of the silica sand substrate.
  • the present invention provides a colored silica sand comprising a silica sand substrate and a colored resin layer coated on the surface of the silica sand substrate, the colored resin layer being cured by a mixture containing the pigment agent, Resin and curing agent.
  • the colored silica sand according to the present invention may be various natural silica sands conventional in the art, such as ore sand, etc.; or may be various kinds of silica sand after manual treatment, such as calcined sand, gas burnt sand, dried sand, Reclaimed sand, etc.
  • the color resin layer is not particularly limited as long as the object of the present invention can be achieved.
  • the color resin layer may preferably have an average thickness of 0.01 to 10 ⁇ m, preferably 0.1. -5 ⁇ .
  • the average thickness of the color resin layer can be calculated by measuring the average particle diameter of the silica sand substrate before and after coating the colored resin layer by a method for measuring the average particle diameter of silica sand known in the art.
  • the resin is not particularly limited as long as the object of the present invention can be achieved, and various resin materials can be used.
  • the resin may be selected from the ring. At least one of an oxyresin, a phenol resin and a furan resin, the resin preferably having a weight average molecular weight of from 300 to 10,000, preferably from 500 to 800.
  • the epoxy resin may have an epoxy value of usually 0.3-0.6 eq/100 g.
  • an epoxy resin E44 having an epoxy value of 0.41-0.47 eq/100 g from Beijing Heli Chemical Co., Ltd.
  • epoxy resin E51 may be used, and the epoxy value is 0.48- 0.54eq/100g of epoxy resin E51, phenolic resin can be used, for example, 939P phenolic resin from Beijing Heli Chemical Co., Ltd., and furan resin can be used, for example, YJ furan resin from Beijing Heli Chemical Co., Ltd., which can be used alone. It can also be used in several combinations.
  • the content of the resin is not particularly limited as long as the object of the present invention can be achieved, and the color of the obtained colored silica sand is long-term stable in order to further improve the bonding strength between the colored resin layer and the silica sand substrate.
  • the resin may be used in an amount of from 0.01 to 10% by weight, based on the weight of the silica sand substrate, preferably from 0.1 to 8% by weight.
  • the resin can be sufficiently contacted with the silica sand substrate to have an average thickness of the colored resin layer of 0.01 to 10 ⁇ m, and on the other hand, the color resin layer and the silica sand substrate can be made. More tightly combined.
  • the colored resin layer may cover only a part of the surface of the silica sand or may cover all of the surface of the silica sand.
  • the silica sand having the color spot or the streak effect can be obtained, and when the surface of the silica sand is completely covered, the silica sand of various colors can be obtained, and of course, the colorfully-sanded silica sand can be obtained at the same time.
  • the coverage area of the colored resin layer is not particularly limited with respect to the surface area of the silica sand substrate, and may be appropriately selected according to actual needs.
  • the coverage of the colored resin layer may be 5 to 100%, preferably 30 to 100%, more preferably 60 to 100%, still more preferably 100% with respect to the surface area of the silica sand substrate.
  • various colored silica sands can be obtained.
  • the content of the curing agent is not particularly limited, and may be selected according to actual needs.
  • the curing agent may be used in an amount of 0.001 to 5% by weight, preferably 0.01-3% by weight.
  • the curing agent is not particularly limited as long as it can achieve the object of the present invention, and various curing agents conventional in the art can be used. In the preferred case, it can be dicyandiamide, adipic acid dihydrazide, acid anhydride, and plural.
  • At least one of a phenol, a polythiol, a resol resin, an amino resin, an aliphatic polyamine, an alicyclic polyamine, a polyamide, a modified aromatic amine, an imidazole, and a boron trifluoride complex are commercially available.
  • the curing causes the pigment agent, the resin and the curing agent to form a colored resin layer on the surface of the silica sand substrate, which can be achieved by bringing the pigment agent, the resin and the curing agent into contact with the silica sand substrate and drying.
  • the curing conditions include: the curing temperature may be 50-100 ° C, and the curing time may be 30-600 s.
  • the pigment agent to be used is not particularly limited as long as it can achieve the purpose of coloring silica sand, and various conventional pigment agents in the art can be generally used.
  • the content of the pigment agent is not particularly limited as long as it can cover the resin layer formed, and can be appropriately selected according to actual needs.
  • the pigment may be used in an amount of from 0.01 to 0.5% by weight, more preferably from 0.1 to 0.3% by weight, based on the weight of the silica sand substrate.
  • the pigment agent used in the colored silica sand of the present invention may contain iron yellow powder and titanium white powder, wherein the iron yellow powder may be contained in an amount of from 1 to 99% by weight based on the total weight of the iron yellow powder and the titanium white powder.
  • the white powder may be present in an amount of from 99 to 1% by weight.
  • the iron yellow powder is contained in an amount of 10 to 30% by weight based on the total weight of the iron yellow powder and the titanium powder
  • the titanium white powder is contained in an amount of 70 to 90% by weight.
  • the content of the iron yellow powder is 14 to 15% by weight based on the total weight of the iron yellow powder and the titanium white powder, and the content of the titanium white powder is 85 to 86% by weight.
  • the silica sand can be easily dyed yellow, and the silica sand is not easily colored after being colored, and the color has good long-term stability.
  • the weight ratio of the iron yellow powder to the titanium white powder may be from 0.02 to 95, more preferably from 0.1 to 10, further preferably from 0.12 to 2. 0.3 is particularly preferably 0.17. Iron yellow powder and titanium white powder in the above mixing ratio When mixed, it can enhance the coloring performance of silica sand and make the color of silica sand more full.
  • the main component of the iron yellow powder is Heston pigment powder, Fe 2 0 3 %>86% by weight, the sieve residue (320 mesh) 0.5% by weight, and the PH value. 3.5-7, can be obtained commercially, such as iron yellow powder of Shanghai Xinyan Pigment Co., Ltd.; titanium dioxide is mainly composed of titanium dioxide, 13 ⁇ 4) 2 % 90% by weight, sieve residue (325 mesh) 0.05% by weight, PH value It is 7.0-9.5, and the average particle size is 0.30 ⁇ , which is commercially available, such as titanium dioxide of Langfang Xiangyu Titanium Dioxide Manufacturing Co., Ltd.
  • the pigment agent may further contain a light stabilizer.
  • the light stabilizer is not particularly limited as long as it can achieve the object of the present invention, and various conventional light stabilizers in the art can be used.
  • it may be at least one of benzophenone, benzotriazole and hindered amine; it may also be at least one of various conventional quenchers and light-shielding agents in the field.
  • the quenching agent is mainly a metal complex such as an organic complex of nickel, cobalt and iron; the light shielding agent mainly comprises carbon black, zinc oxide, titanium oxide and zinc antimony.
  • the amount of the light stabilizer to be added is not particularly limited, and can be appropriately selected as long as the object of the present invention can be achieved.
  • the content of the light stabilizer may be from 0.01 to 50% by weight, preferably from 0.01 to 20% by weight, based on the total weight of the pigment agent, further It is preferably from 1 to 10% by weight.
  • the present invention also provides a method for preparing the above colored silica sand, wherein the method comprises: mixing a silica sand substrate with a resin at 100-200 ° C, and then mixing the silica sand substrate and the resin with the pigment agent and curing The agent contacts to form a colored resin layer on the surface of the silica sand substrate.
  • the silica sand substrate before mixing with the resin may be heat-treated at 250-1000 ° C for 1-60 min, more preferably at 400-800 ° C for 15-30 min, after the silica sand is heat-treated at the above temperature.
  • the impurities on the surface of the silica sand can be sufficiently removed, and the silica sand substrate can be closely bonded to the colored resin layer.
  • the heat treated silica sand substrate is transferred to the sand mixing In the machine, and naturally stirred to a temperature of 100-200 ° C under stirring at a stirring speed of 50-200 r / min, the resin is added, and the stirring is continued until the mixing is uniform, that is, a homogeneous mixture of the silica sand substrate and the resin is obtained.
  • the amount of the resin to be used is not particularly limited as long as the object of the present invention can be attained, and in order to further improve the bonding strength between the colored resin layer and the silica sand substrate, the color long-term stability of the obtained colored silica sand is improved, and in the preferred case,
  • the resin may be used in an amount of from 0.01 to 10% by weight, based on the weight of the silica sand substrate, preferably from 0.1 to 8% by weight.
  • the amount of the resin is in the above range, on the one hand, the resin can be sufficiently contacted with the silica sand substrate, and the average thickness of the colored resin layer is 0.01-10 ⁇ , and on the other hand, the colored resin layer and the silica sand substrate can be made. More tightly combined.
  • the pigment agent to be used in the contact, there is no particular requirement as long as the pigment agent to be used can achieve the purpose of coloring silica sand, and various conventional pigments in the art can be generally used.
  • the content of the pigment agent is not particularly limited as long as the formed color resin layer can cover the resin layer, and can be appropriately selected according to actual needs.
  • the amount of the pigment agent may preferably be from 0.01 to 0.5% by weight, and more preferably from 0.1 to 0.3% by weight, based on the weight of the silica sand substrate.
  • the pigment agent used in the method of the present invention may contain iron yellow powder and titanium white powder, wherein the iron yellow powder may be contained in an amount of from 1 to 99% by weight based on the total weight of the iron yellow powder and the titanium white powder.
  • the white powder may be present in an amount of from 99 to 1% by weight.
  • the iron yellow powder is contained in an amount of 10 to 30% by weight based on the total weight of the iron yellow powder and the titanium white powder
  • the titanium white powder is contained in an amount of 70 to 90% by weight.
  • the content of the iron yellow powder is 14 to 15% by weight based on the total weight of the iron yellow powder and the titanium powder
  • the content of the titanium white powder is 85 to 86% by weight.
  • the weight ratio of iron yellow powder to titanium white powder may be from 0.02 to 95, more preferably from 0.1 to 10, further preferably. It is 0.12-0.3, and particularly preferably 0.17.
  • the iron yellow powder and the titanium white powder are mixed at the above mixing ratio, the coloring property to the silica sand can be enhanced, and the color after the silica sand is colored More full.
  • the main component of iron yellow powder is Heston pigment powder, ? 6 2 0 3 % ⁇ 86% by weight, sieve residue (320 mesh) 0.5% by weight, pH value 3.5-7, commercially available, such as iron yellow powder of Shanghai Xinyan Pigment Co., Ltd.; main component of titanium dioxide It is titanium dioxide, 13 ⁇ 4) 2 % 90% by weight, sieve residue (325 mesh) 0.05% by weight, PH value 7.0-9.5, average particle size 0.30 ⁇ , which can be obtained by commercial, such as Langfang Xiangyu Titanium Dioxide Manufacturing Co., Ltd. Titanium dioxide.
  • the pigment agent may further contain a light stabilizer.
  • the light stabilizer is not particularly limited as long as it can achieve the object of the present invention, and various conventional light stabilizers in the art can be used.
  • it may be at least one of benzophenone, benzotriazole and hindered amine; it may also be at least one of various conventional quenchers and light-shielding agents in the art.
  • the quenching agent is mainly a metal complex, such as an organic complex of nickel, cobalt, iron, etc.;
  • the light shielding agent mainly includes carbon black, zinc oxide, titanium oxide and zinc lanthanum. These light stabilizers are commercially available.
  • the amount of the light stabilizer to be added is not particularly limited, and can be appropriately selected as long as the object of the present invention can be achieved.
  • the content of the light stabilizer may be from 0.01 to 50% by weight, preferably from 0.01 to 20% by weight, based on the total weight of the pigment agent, further It is preferably from 1 to 10% by weight.
  • the contact temperature may be 50-200 ° C, and the contact time may be It is 30-600s.
  • the color silica sand obtained can be made more full and lustrous.
  • the contacting may be carried out under stirring at a stirring speed of 50 to 200 r/min.
  • a method for preparing colored silica sand according to the present invention in order to make a pigment and a curing agent and a silica sand substrate
  • the mixture of the resins is more sufficiently contacted.
  • the pigment agent is first contacted with the mixture of the silica sand substrate and the resin for 10 to 100 s before the curing agent is added.
  • the amount of the curing agent is not particularly limited and may be selected according to actual needs. In order to more fully cure the colored resin layer, preferably, the amount of the curing agent may be based on the weight of the silica sand substrate. It is 0.001 to 5% by weight.
  • the curing can be carried out under stirring at a stirring speed of 50 to 200 r/min.
  • the curing agent is not particularly limited as long as it can achieve the object of the present invention, and various curing agents conventional in the art can be used, and in the preferred case, it can be dicyandiamide, adipic acid dihydrazide, acid anhydride, and plural. At least one of a phenol, a polythiol, a resol resin, an amino resin, an aliphatic polyamine, an alicyclic polyamine, a polyamide, a modified aromatic amine, an imidazole, and a boron trifluoride complex. These curing agents are commercially available.
  • the method further comprises adding a lubricant further after the colored resin layer is cured.
  • the lubricant may be used in an amount of 0.0001 to 1% by weight, more preferably 0.1 to 1% by weight.
  • the lubricant is not particularly required, and various conventional lubricants in the art can be used, and for example, it may be stearates, mineral oils, synthetic oils, animal and vegetable oils, and water-based liquids. At least one of them.
  • the stearate include sodium stearate and calcium stearate.
  • mineral oil examples include distillate mineral oil, residual lubricating oil, and blending lubricating oil.
  • animal and vegetable oils include whale oil, vegetable oil, and tea.
  • Oil, castor oil, etc., and water-based liquids include water, emulsions, mixtures of water and ethylene glycol, and the like.
  • the above lubricants are all well known to those skilled in the art and are commercially available.
  • the colored resin layer and the silica sand can be tightly combined, the color long-term stability of the colored silica sand is greatly improved, and the effect of not discoloring or fading for a long time can be achieved.
  • the preparation method of the colored silica sand can be used for preparing various colored silica sands, and is further used for preparing various building materials formed by colored silica sand, for example, when preparing sand-based permeable bricks, etc., by using the colored silica sand of the present invention, You can get permeable bricks of various colors to realize the permeable brick Diversify colors and improve the aesthetics of permeable bricks.
  • the silica sand substrate used was silica sand purchased from the Naimer No. 6 sand mill in Inner Mongolia, and the resin used was purchased from Beijing Heli Chemical Co., Ltd., and the pigment used was purchased from Shanghai. Xinyan Pigment Co., Ltd. used the curing agent from Shanghai Ousheng Chemical Co., Ltd. The lubricant used was purchased from Qingdao Dehui Fine Chemical Co., Ltd.
  • This embodiment is for explaining the colored silica sand of the present invention and a preparation method thereof.
  • Color silica sand was prepared in accordance with the method of Example 1, except that no epoxy resin or resol was added during the preparation of the colored silica sand.
  • Example 2
  • This embodiment is for explaining the colored silica sand of the present invention and a preparation method thereof.
  • This embodiment is for explaining the colored silica sand of the present invention and a preparation method thereof.
  • silica sand 100kg was added to the muffle furnace, calcined at 1000 ° C for 1 min, and then the calcined silica sand was directly transferred to the sand mixer, and cooled to 200 ° C at a stirring speed of 200 r / min.
  • 10kg epoxy resin adhesive (model E51, epoxy value 0.48-0.54eq/100g), continue to stir, to obtain a homogeneous mixture of epoxy resin and silica sand.
  • 0.01 kg of CR-826 titanium dioxide was added to the mixture at a temperature of 200 ° C, and after stirring for 10 s, 5 kg of resole phenolic resin was added.
  • This embodiment is for explaining the colored silica sand of the present invention and a preparation method thereof.
  • This embodiment is for explaining the colored silica sand of the present invention and a preparation method thereof.
  • silica sand 100kg was added to the muffle furnace, calcined at 600 ° C for 30 min, and then the calcined silica sand was directly transferred to the sand mixer. At a stirring speed of 120 r / min, it was cooled to 160 ° C, and lkg was added.
  • Epoxy resin adhesive (model E51, epoxy value 0.48-0.54eq/100g), continue to stir, to obtain a homogeneous mixture of epoxy resin and silica sand.
  • This embodiment is for explaining the colored silica sand of the present invention and a preparation method thereof.
  • the xenon arc radiation test was carried out on the colored silica sands obtained in Examples 1-6 and Comparative Example 1 according to GB/T1865-1997 using a xenon lamp aging test box (Beijing Hongda Tianmo Test Equipment Co., Ltd., model SN-500). The weatherability of the colored silica sand was tested.
  • Example 7 It can be seen from the test results in Table 1 that the colored silica sand obtained in Comparative Example 1 is unevenly colored or has a color change after the xenon arc radiation test.
  • the colored silica sand obtained by the method for preparing colored silica sand of the present invention has good apparent color and weather resistance.
  • the colored silica sand of the present invention has good long-term color stability.
  • the color silica sand of the present invention has a simple preparation method and is easy to be applied industrially.
  • This embodiment is for explaining the colored silica sand of the present invention and a preparation method thereof.
  • silica sand surface pretreatment step 100kg silica sand is added to the muffle furnace, calcined at 800 ° C for 20 min, and then the calcined silica sand is directly transferred to the sand mixer, at a stirring speed of lOOr / min, When cooling to 150 °C, add 5kg epoxy resin binder (E51, epoxy value 0.48-0.54eq/100g) and continue to stir.
  • epoxy resin binder epoxy resin binder
  • silica sand coloring step Add 0.2 kg of pigment C1 to the silica sand in step (1) at a temperature of 100 ° C, stir for 60 s, add lkg resole (model 2127), continue stirring for 300 s. Thereafter, 0.5 kg of mineral oil (Model X11644) was added, and the mixture was uniformly stirred to obtain colored silica sand.
  • Example 8 Silica sand coloring step: Add 0.2 kg of pigment C1 to the silica sand in step (1) at a temperature of 100 ° C, stir for 60 s, add lkg resole (model 2127), continue stirring for 300 s. Thereafter, 0.5 kg of mineral oil (Model X11644) was added, and the mixture was uniformly stirred to obtain colored silica sand.
  • This embodiment is for explaining the colored silica sand of the present invention and a preparation method thereof.
  • the pigment preparation (C2) was prepared in the same manner as in Example 7, except that the composition of the pigment preparation was as shown in Table 2.
  • Silica sand surface pretreatment step 100kg silica sand is added to the muffle furnace, calcined at 1000 ° C for 1 min, and then the calcined silica sand is directly transferred to the sand mixer, at a stirring speed of 200 r / min, When cooling to 200 ° C, 10 kg of epoxy resin adhesive (model E51, epoxy value 0.48-0.54eq/100g) was added and stirring was continued.
  • epoxy resin adhesive model E51, epoxy value 0.48-0.54eq/100g
  • Silica sand coloring step 0.01 kg of pigment agent C2 is added to the silica sand in step (1) at a temperature of 200 ° C, and after stirring for 10 s, 5 kg of resole phenolic resin (model 2127) is added, and stirring is continued for 600 s. Add lkg mineral oil (model: X11644) and mix well to obtain colored silica sand.
  • Example 9 Silica sand coloring step: 0.01 kg of pigment agent C2 is added to the silica sand in step (1) at a temperature of 200 ° C, and after stirring for 10 s, 5 kg of resole phenolic resin (model 2127) is added, and stirring is continued for 600 s. Add lkg mineral oil (model: X11644) and mix well to obtain colored silica sand.
  • This embodiment is for explaining the colored silica sand of the present invention and a preparation method thereof.
  • the pigment preparation (C3) was prepared in the same manner as in Example 7, except that the composition of the pigment preparation was as shown in Table 2.
  • Silica sand surface pretreatment step 100 kg of silica sand is added to a muffle furnace, calcined at 250 ° C for 60 min, and then the calcined silica sand is directly transferred to a sand mixer, at a stirring speed of 50 r / min, When cooling to 100 ° C, 0.01 kg of epoxy resin adhesive (model E51, epoxy value 0.48-0.54 eq/100 g) was added and stirring was continued.
  • epoxy resin adhesive model E51, epoxy value 0.48-0.54 eq/100 g
  • Silica sand coloring step 0.5 kg of pigment agent C3 is added to the silica sand in step (1) at a temperature of 50 ° C, and after stirring for 30 s, 0.001 kg of resole phenolic resin (model 2127) is added, and stirring is continued for 100 s. After that, add 0.0001 kg of mineral oil (model: X11644), and mix well to obtain colored silica sand.
  • Example 10 Silica sand coloring step: 0.5 kg of pigment agent C3 is added to the silica sand in step (1) at a temperature of 50 ° C, and after stirring for 30 s, 0.001 kg of resole phenolic resin (model 2127) is added, and stirring is continued for 100 s. After that, add 0.0001 kg of mineral oil (model: X11644), and mix well to obtain colored silica sand.
  • mineral oil model: X11644
  • This embodiment is for explaining the colored silica sand of the present invention and a preparation method thereof.
  • a pigment preparation (C4) was prepared in accordance with the method of Example 7, except that the composition of the pigment preparation was as shown in Table 2.
  • Silica sand surface pretreatment step 100 kg of silica sand is added to a muffle furnace, calcined at 600 ° C for 20 min, and then the calcined silica sand is directly transferred to a sand mixer, at a stirring speed of 120 r / min, When cooled to 160 ° C, add lkg epoxy resin adhesive (model E51, epoxy value 0.48-0.54eq/100g) and continue to stir.
  • Silica sand coloring step 0.2 kg of pigment agent C4 is added to the silica sand in step (1) at a temperature of 120 ° C, and after stirring for 100 s, 0.1 kg of resole phenolic resin (model 2127) is added, and stirring is continued 480. After that, add 0.1kg of mineral oil (model: X11644), stir evenly, then get color Silica sand.
  • Example 11 Silica sand coloring step: 0.2 kg of pigment agent C4 is added to the silica sand in step (1) at a temperature of 120 ° C, and after stirring for 100 s, 0.1 kg of resole phenolic resin (model 2127) is added, and stirring is continued 480. After that, add 0.1kg of mineral oil (model: X11644), stir evenly, then get color Silica sand.
  • mineral oil model: X11644
  • This embodiment is for explaining the colored silica sand of the present invention and a preparation method thereof.
  • a pigment preparation (C5) was prepared in accordance with the method of Example 7, except that the composition of the pigment preparation was as shown in Table 2.
  • Silica sand surface pretreatment step 100kg silica sand is added to the muffle furnace, calcined at 400 ° C for 25 min, and then the calcined silica sand is directly transferred to the sand mixer, at a stirring speed of 80 r / min, When cooling to 120 ° C, 6 kg of epoxy resin adhesive (model E51, epoxy value 0.48-0.54eq/100g) was added and stirring was continued.
  • epoxy resin adhesive model E51, epoxy value 0.48-0.54eq/100g
  • Silica sand coloring step adding 0.2 kg of pigment agent C5 to the silica sand in step (1) at a temperature of 80 ° C, stirring for 60 s, adding 3 kg of resole phenolic resin (model 2127), and stirring for 180 s. Add 0.6kg of mineral oil (model: XI 1644) and mix well to obtain colored silica sand.
  • Example 12 Silica sand coloring step: adding 0.2 kg of pigment agent C5 to the silica sand in step (1) at a temperature of 80 ° C, stirring for 60 s, adding 3 kg of resole phenolic resin (model 2127), and stirring for 180 s. Add 0.6kg of mineral oil (model: XI 1644) and mix well to obtain colored silica sand.
  • This embodiment is for explaining the colored silica sand of the present invention and a preparation method thereof.
  • a pigment preparation (C6) was prepared in accordance with the method of Example 7, except that the composition of the pigment preparation was as shown in Table 2.
  • Silica sand surface pretreatment step 100kg silica sand is added to the muffle furnace, calcined at 800 ° C for 20 min, and then the calcined silica sand is directly transferred to the sand mixer, at a stirring speed of lOOr / min, When cooling to 150 °C, add 5kg epoxy resin adhesive (E51, epoxy value) 0.48-0.54eq/100g), continue to stir.
  • Silica sand coloring step Add 0.2 kg of pigment C6 to the silica sand in step (1) at a temperature of 100 ° C, stir for 60 s, add lkg resole phenolic resin (model 2127), continue stirring for 300 s. Thereafter, 0.5 kg of mineral oil (Model X11644) was added, and the mixture was uniformly stirred to obtain colored silica sand.
  • Example 13 Silica sand coloring step: Add 0.2 kg of pigment C6 to the silica sand in step (1) at a temperature of 100 ° C, stir for 60 s, add lkg resole phenolic resin (model 2127), continue stirring for 300 s. Thereafter, 0.5 kg of mineral oil (Model X11644) was added, and the mixture was uniformly stirred to obtain colored silica sand.
  • This embodiment is for explaining the colored silica sand of the present invention and a preparation method thereof.
  • a pigment preparation (C7) was prepared in accordance with the method of Example 7, except that the composition of the pigment preparation was as shown in Table 2.
  • Silica sand surface pretreatment step 100kg silica sand is added to the muffle furnace, calcined at 800 ° C for 20 min, and then the calcined silica sand is directly transferred to the sand mixer, at a stirring speed of lOOr / min, When cooling to 150 °C, add 5kg epoxy resin binder (E51, epoxy value 0.48-0.54eq/100g) and continue to stir.
  • epoxy resin binder epoxy resin binder
  • Silica sand coloring step Add 0.2 kg of pigment C7 to the silica sand in step (1) at a temperature of 100 ° C, stir for 60 s, add lkg resole resin (model 2127), continue stirring for 300 s. Thereafter, 0.5 kg of mineral oil (Model X11644) was added, and the mixture was uniformly stirred to obtain colored silica sand. Silica sand coloring effect test
  • Example 7-13 The colored silica sand obtained in Example 7-13 was used for visual observation, and the case where the color was uniform and there was no untinted silica sand was expressed as ⁇ , and conversely, it was represented as X.
  • the test results are shown in Table 3.
  • Example 7-13 Use xenon lamp aging test box (Beijing Hongda Tianmao Test Equipment Co., Ltd., model number SN-500), according to GB/T1865-1997, the colored silica sand obtained in Example 7-13 was subjected to xenon arc radiation test to test the weather resistance of the colored silica sand.
  • the colored silica sand of the present invention has good long-term color stability, and the color silica sand of the present invention has a simple preparation method and is easy to be industrially applied.

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Description

一种彩色硅砂及其制备方法
技术领域
本发明涉及一种彩色硅砂及其制备方法。 背景技术
硅砂, 又称石英砂, 是一种坚硬、 耐磨、 化学性能稳定的硅酸盐矿物, 粒径为 0.020mm-3.350mm, 其主要矿物成分是二氧化硅,硅砂的颜色为乳白 色或无色半透明状, 硬度为 7, 相对密度为 2.65, 硅砂的化学、 热学和机械 性能具有明显的异向性。 由于硅砂所具有的独特的物理、 化学特性, 而广 泛应用于玻璃、 铸造、 陶瓷、 冶金、 建筑、 化工等众多领域。
天然硅砂资源丰富,常见的有例如风积沙、河沙和海沙等,且价格低廉, 在建筑材料领域中常用作一些沙基透水砖、透水路面等的透水性材料的主要 原料, 但是这些天然硅砂的颜色单一, 在作为建筑材料应用时已不能满足现 代多彩建筑材料的需求。 并且, 通过普通方法对硅砂染色时, 由于硅砂的特 殊性能,很难使硅砂着色,更难获得着色后颜色长期稳定性良好的彩色硅砂。 发明内容
本发明的目的在于克服现有技术中硅砂颜色单一、着色困难以及着色后 颜色长期稳定性差的问题, 提供一种容易着色和着色后颜色长期稳定性好的 彩色硅砂以及其制备方法。
本发明提供了一种彩色硅砂,该彩色硅砂包括硅砂基材和包覆在硅砂基 材表面的彩色树脂层, 所述彩色树脂层是由一种混合物固化而成, 所述混合 物含有颜料剂、 树脂和固化剂。
本发明还提供了一种上述彩色硅砂的制备方法, 其中, 该方法包括: 将硅砂基材在 100-200 °C下与树脂混合均匀, 然后使硅砂基材和树脂的 混合物与颜料剂和固化剂接触, 在硅砂基材表面形成彩色树脂层。
本发明通过在硅砂基材的表面包覆一层彩色树脂层, 能够实现硅砂的多 彩化, 并且由于树脂具有良好的物化性能, 能够维持所得彩色硅砂的颜色长 期稳定性。 另外, 本发明的彩色硅砂的制备方法通过将硅砂基材在 100-200 °C下与树脂混合均匀,然后使硅砂基材和树脂的混合物与颜料剂和固化剂接 触, 在硅砂基材表面形成彩色树脂层, 从而能够使硅砂基材与彩色树脂层更 紧密地结合在一起, 从而避免了颜色脱落的问题, 保证了颜料在硅砂基材表 面的长期稳定性。 具体实施方式
本发明提供了一种彩色硅砂,该彩色硅砂包括硅砂基材和包覆在硅砂基 材表面的彩色树脂层, 所述彩色树脂层是由一种混合物固化而成, 所述混合 物含有颜料剂、 树脂和固化剂。
根据本发明的彩色硅砂,作为硅砂基材可以是本领域常规的各种天然硅 砂, 如矿砂等; 也可以是经过人工处理后的各种硅砂, 如焙烧砂、 气烧砂、 烘干砂、 再生砂等。 彩色树脂层只要能够实现本发明的目的, 就没有特别的 限定, 为了进一步提高彩色硅砂的颜色长期稳定性, 在优选的情况下, 彩色 树脂层的平均厚度可以为 0.01-10 μηι, 优选为 0.1-5 μηι。 彩色树脂层的平均 厚度在上述范围内时, 一方面能够保证表现出充分的色彩效果, 另一方面还 可以保证彩色树脂层与硅砂基材之间的结合强度。彩色树脂层的平均厚度可 以利用本领域公知的硅砂平均粒径测定方法,通过分别测定硅砂基材在包覆 彩色树脂层前后的平均粒径来计算得到。
根据本发明的彩色硅砂, 所述树脂只要能够实现本发明的目的, 就没有 特别的限定, 可以使用各种树脂材料, 在优选的情况下, 树脂可以为选自环 氧树脂、 酚醛树脂和呋喃树脂中的至少一种, 所述树脂的重均分子量通常可 以为 300-10000, 优选为 500-800。 环氧树脂的环氧值通常可以为 0.3-0.6eq/100g, 例如可以使用购自北京合力化工有限公司的环氧值为 0.41-0.47eq/100g 的环氧树脂 E44, 环氧值为 0.48-0.54eq/100g 的环氧树脂 E51 , 酚醛树脂可以使用例如购自北京合力化工有限公司的 939P酚醛树脂, 呋喃树脂可以使用例如购自北京合力化工有限公司的 YJ呋喃树脂, 这些树 脂可以单独使用一种, 也可以几种组合使用。
根据本发明的彩色硅砂, 所述树脂的含量只要能够实现本发明的目的, 就没有特别的限定, 为了进一步提高彩色树脂层与硅砂基材之间的结合强 度, 提高所得彩色硅砂的颜色长期稳定性, 在优选的情况下, 以硅砂基材的 重量为基准, 所述树脂的用量可以为 0.01-10重量%, 优选为 0.1-8重量%。 所述树脂的含量在上述范围内时, 一方面能够保证树脂与硅砂基材充分接 触, 使彩色树脂层的平均厚度为 0.01-10 μηι, 另一方面还可以使彩色树脂层 与硅砂基材之间更紧密地结合。
另外, 在本发明的彩色硅砂中, 彩色树脂层可以只覆盖硅砂表面的一部 分,也可以覆盖硅砂表面的全部。在彩色树脂层只覆盖硅砂表面的一部分时, 可以得到彩色斑点或斑紋效果的硅砂, 而全部覆盖硅砂表面时, 可以得到各 种色彩的硅砂, 当然此时也同样可以得到多彩斑紋的硅砂。相对于硅砂基材 表面积, 彩色树脂层的覆盖面积没有特别的限定, 可以根据实际需要而适当 选择。 在优选的情况下, 相对于硅砂基材的表面积, 所述彩色树脂层的覆盖 率可以为 5-100%,优选为 30-100%,更优选为 60-100%,进一步优选为 100%。 在上述优选的情况下, 可以得到各种色彩斑斓的彩色硅砂。
根据本发明的彩色硅砂, 所述固化剂的含量没有特别的限定, 可以根据 实际需要进行选择, 为了使彩色树脂层更充分地固化, 在优选的情况下, 以 硅砂基材的重量为基准, 所述固化剂的用量可以为 0.001-5重量%, 优选为 0.01-3重量%。 所述固化剂只要能够实现本发明的目的, 就没有特别要求, 可以使用本领域常规的各种固化剂, 在优选的情况下, 可以为双氰胺、 己二 酸二酰肼、 酸酐、 多元酚、 聚硫醇、 甲阶酚醛树脂、 氨基树脂、 脂肪族多胺、 脂环族多胺、 聚酰胺、 改性芳胺、 咪唑以及三氟化硼络合物中的至少一种。 这些固化剂均可通过商购得到。
根据本发明的彩色硅砂, 所述固化使得颜料剂、树脂和固化剂在硅砂基 材表面形成彩色树脂层, 所述固化可以通过将颜料剂、 树脂和固化剂与硅砂 基材接触并干燥来实现, 所述固化的条件包括: 固化温度可以为 50-100 °C, 固化时间可以为 30-600s。
根据本发明的彩色硅砂, 所使用的颜料剂只要能够实现硅砂着色的目 的, 就没有特别的要求, 通常可以使用本领域中各种常规的颜料剂。 对于所 述颜料剂的含量只要能够使所形成的彩色树脂层覆盖树脂层就没有特别的 限定, 可以根据实际需要适当地选择。 在优选情况下, 以硅砂基材的重量为 基准, 颜料剂的用量可以为 0.01-0.5重量%, 进一步优选为 0.1-0.3重量%。 在优选的情况下, 本发明的彩色硅砂使用的颜料剂可以含有铁黄粉和钛白 粉, 其中, 以铁黄粉和钛白粉的总重量为基准, 铁黄粉的含量可以为 1-99 重量%, 钛白粉的含量可以为 99-1重量%。 在优选的情况下, 以铁黄粉和钛 白粉的总重量为基准,铁黄粉的含量为 10-30重量%,钛白粉的含量为 70-90 重量%。 在进一步优选的情况下, 以铁黄粉和钛白粉的总重量为基准, 铁黄 粉的含量为 14-15重量%, 钛白粉的含量为 85-86重量%。 铁黄粉和钛白粉 以上述范围内的混合物使用时, 能够容易地将硅砂染成黄色, 且硅砂着色后 不易掉色, 颜色长期稳定性良好。
根据本发明的彩色硅砂, 为了使颜料剂与硅砂更易紧密结合, 在进一步 优选的情况下, 铁黄粉和钛白粉的重量比可以为 0.02-95, 更优选为 0.1-10, 进一步优选为 0.12-0.3, 特别优选为 0.17。 铁黄粉和钛白粉以上述混合比例 混合时, 能够增强对硅砂的着色性能, 使硅砂着色后的色彩更加饱满。
根据本发明的彩色硅砂, 其中, 铁黄粉 (氧化铁黄) 的主要成分为赫斯 顿颜料粉, Fe203%>86重量%,筛余物 (320目 ) 0.5重量%, PH值为 3.5-7, 可以通过商购得到, 比如上海新艳颜料有限公司的铁黄粉; 钛白粉的主要成 分为二氧化钛, 1¾)2% 90重量%, 筛余物 (325目) 0.05重量%, PH值 为 7.0-9.5, 平均粒径 0.30μηι, 可以通过商购得到, 比如廊坊翔宇钛白粉制 造有限公司的钛白粉。
根据本发明的彩色硅砂, 为了提高硅砂着色后色彩的长时间稳定性, 在 进一步优选的情况下, 所述颜料剂中还可以含有光稳定剂。 光稳定剂只要能 够实现本发明的目的, 就没有特别的限定, 可以使本领域各种常规的光稳定 剂。 例如可以是二苯甲酮、 苯并三唑和受阻胺中的至少一种; 也可以是本领 域各种常规的猝灭剂和光屏蔽剂中的至少一种。 其中, 猝灭剂主要是金属络 合物, 例如镍、 钴、 铁的有机络合物等; 光屏蔽剂主要有炭黑、 氧化锌、 二 氧化钛和锌钡等。 这些光稳定剂均可通过商购得到。
光稳定剂的添加量没有特别的限定, 只要能够实现本发明的目的, 在实 际中可以适当选择。 为了充分提高彩色硅砂的颜色长时间稳定性, 在进一步 优选的情况下, 以颜料剂的总重量为基准, 光稳定剂的含量可以为 0.01-50 重量%, 优选为 0.01-20重量%, 进一步优选为 1-10重量%。
本发明还提供了一种上述彩色硅砂的制备方法, 其中, 该方法包括: 将硅砂基材在 100-200 °C下与树脂混合均匀, 然后使硅砂基材和树脂的 混合物与颜料剂和固化剂接触, 在硅砂基材表面形成彩色树脂层。
在优选的情况下,可以将与树脂混合前的硅砂基材在 250-1000 °C下热处 理 l-60min, 更优选在 400-800°C下加热 15-30min, 硅砂经过上述温度下的 热处理后, 能够将硅砂表面的杂质充分除去, 能够促进硅砂基材与彩色树脂 层紧密地结合。在进一步优选的情况下, 将热处理后的硅砂基材转移至混砂 机中, 并在搅拌速度为 50-200r/min的搅拌下自然冷却至 100-200 °C, 加入树 脂, 继续搅拌至混合均匀, 即得到硅砂基材和树脂的均匀混合物。 所述树脂 的用量只要能够实现本发明的目的, 就没有特别的限定, 为了进一步提高彩 色树脂层与硅砂基材之间的结合强度, 提高所得彩色硅砂的颜色长期稳定 性, 在优选的情况下, 以硅砂基材的重量为基准, 所述树脂的用量可以为 0.01-10重量%, 优选为 0.1-8重量%。 所述树脂的用量在上述范围内时, 一 方面能够保证树脂与硅砂基材充分接触,使彩色树脂层的平均厚度为 0.01-10 μηι, 另一方面还可以使彩色树脂层与硅砂基材之间的更紧密地结合。
按照本发明的彩色硅砂的制备方法, 在所述接触中, 对于所使用的颜料 剂只要能够实现硅砂着色的目的, 就没有特别的要求, 通常可以使用本领域 中各种常规的颜料。对于所述颜料剂的含量只要能够使所形成的彩色树脂层 覆盖树脂层就没有特别的限定, 可以根据实际需要适当地选择。 在优选情况 下, 以硅砂基材的重量为基准, 颜料剂的用量可以优选为 0.01-0.5重量%, 进一步优选为 0.1-0.3重量%。在优选的情况下, 本发明的方法中使用的颜料 剂可以含有铁黄粉和钛白粉, 其中, 以铁黄粉和钛白粉的总重量为基准, 铁 黄粉的含量可以为 1-99重量%, 钛白粉的含量可以为 99-1重量%。 在优选 的情况下, 以铁黄粉和钛白粉的总重量为基准, 铁黄粉的含量为 10-30重量 %, 钛白粉的含量为 70-90重量%。 在进一步优选的情况下, 以铁黄粉和钛 白粉的总重量为基准,铁黄粉的含量为 14-15重量%,钛白粉的含量为 85-86 重量%。 铁黄粉和钛白粉以上述范围内的混合物使用时, 能够容易地将硅砂 染成黄色, 且硅砂着色后不易掉色, 颜色长期稳定性良好。
按照本发明的彩色硅砂的制备方法, 为了使颜料剂与硅砂更易紧密结 合, 在进一步优选的情况下, 铁黄粉和钛白粉的重量比可以为 0.02-95, 更 优选为 0.1-10, 进一步优选为 0.12-0.3, 特别优选为 0.17。 铁黄粉和钛白粉 以上述混合比例混合时, 能够增强对硅砂的着色性能, 使硅砂着色后的色彩 更加饱满。
按照本发明的彩色硅砂的制备方法, 其中, 铁黄粉 (氧化铁黄) 的主要 成分为赫斯顿颜料粉, ?6203%≥86重量%, 筛余物 (320目) 0.5重量%, PH值为 3.5-7, 可以通过商购得到, 比如上海新艳颜料有限公司的铁黄粉; 钛白粉的主要成分为二氧化钛, 1¾)2% 90重量%, 筛余物(325目) 0.05 重量%, PH值为 7.0-9.5, 平均粒径 0.30μηι, 可以通过商购得到, 比如廊 坊翔宇钛白粉制造有限公司的钛白粉。
按照本发明的彩色硅砂的制备方法,为了提高硅砂着色后色彩的长时间 稳定性, 在进一步优选的情况下, 所述颜料剂中还可以含有光稳定剂。 光稳 定剂只要能够实现本发明的目的, 就没有特别的限定, 可以使本领域各种常 规的光稳定剂。 例如可以是二苯甲酮、 苯并三唑和受阻胺中的至少一种; 也 可以是本领域各种常规的猝灭剂和光屏蔽剂中的至少一种。 其中, 猝灭剂主 要是金属络合物, 例如镍、 钴、 铁的有机络合物等; 光屏蔽剂主要有炭黑、 氧化锌、 二氧化钛和锌钡等。 这些光稳定剂均可通过商购得到。
光稳定剂的添加量没有特别的限定, 只要能够实现本发明的目的, 在实 际中可以适当选择。 为了充分提高彩色硅砂的颜色长时间稳定性, 在进一步 优选的情况下, 以颜料剂的总重量为基准, 光稳定剂的含量可以为 0.01-50 重量%, 优选为 0.01-20重量%, 进一步优选为 1-10重量%。
按照本发明的彩色硅砂的制备方法,为了使彩色树脂层能够更好地与硅 砂基材结合在一起, 在优选的情况下, 所述接触的温度可以为 50-200°C, 接 触的时间可以为 30-600s。 在上述条件下使颜料剂和固化剂与硅砂基材接触 时, 可以使得到的彩色硅砂的颜色更加饱满且具有光泽。 为了在短时间内使 颜料在硅砂基材和树脂的混合物中均匀分散, 在进一步优选的情况下, 所述 接触可以在搅拌速度为 50-200r/min的搅拌下进行。
按照本发明的彩色硅砂的制备方法,为了使颜料和固化剂与硅砂基材和 树脂的混合物更充分地接触, 在更优选的情况下, 使颜料剂先与硅砂基材和 树脂的混合物接触 10-lOOs后再加入固化剂。 所述固化剂的用量没有特别的 限定, 可以根据实际需要进行选择, 为了使彩色树脂层更充分地固化, 在优 选的情况下, 以硅砂基材的重量为基准, 所述固化剂的用量可以为 0.001-5 重量%。 为了均匀固化, 所述固化可以在搅拌速度为 50-200r/min 的搅拌下 进行。 所述固化剂只要能够实现本发明的目的, 就没有特别要求, 可以使用 本领域常规的各种固化剂,在优选的情况下,可以为双氰胺、 己二酸二酰肼、 酸酐、 多元酚、 聚硫醇、 甲阶酚醛树脂、 氨基树脂、 脂肪族多胺、 脂环族多 胺、 聚酰胺、 改性芳胺、 咪唑以及三氟化硼络合物中的至少一种。 这些固化 剂均可通过商购得到。
按照本发明的彩色硅砂的制备方法,为了使得到的彩色硅砂具有良好的 流动性, 在进一步优选的情况下, 该方法还包括在彩色树脂层固化后, 进一 步加入润滑剂。 所述润滑剂的用量可以为 0.0001-1 重量%, 更优选为 0.1-1 重量%。 另外, 只要能够实现本发明的目的, 所述润滑剂没有特别的要求, 可以使用本领中的各种常规润滑剂,例如可以为硬脂酸盐、矿物油、合成油、 动植物油和水基液体中的至少一种。 其中, 硬脂酸盐可以举出硬脂酸钠、 硬 脂酸钙等, 矿物油可举出馏分矿物油、 残渣润滑油、 调合润滑油等, 动植物 油可举出鲸鱼油、 菜油、 茶油、 蓖麻油等, 水基液体可举出水、 乳化液、 水 与乙二醇及其它物质的混合物等。 上述润滑剂均均为本领域人员所熟知, 可 通过商购所得到。
按照本发明的彩色硅砂的制备方法, 能够使彩色树脂层与硅砂紧密地结 合在一起,大大提高了彩色硅砂的颜色长期稳定性,能够实现长时间不变色、 不掉色的效果。 该彩色硅砂的制备方法可以用于各种彩色硅砂的制备, 进而 用于制备由彩色硅砂所形成的各种建筑材料等, 如在制备沙基透水砖等时, 通过使用本发明的彩色硅砂, 可以得到各种色彩的透水砖, 实现透水砖的颜 色多样化, 提高透水砖的美观度。
以下, 通过实施例对本发明的彩色硅砂及其制备方法进一步说明, 但本 发明并不限于以下各实施例。
在以下的各实施例和对比例中,所使用的硅砂基材为购自内蒙奈曼第六 砂厂的硅砂, 所使用的有树脂购自北京合力化工有限公司, 所使用的颜料购 自上海新艳颜料公司, 所使用的固化剂购自上海欧盛化工有限公司, 所使用 的润滑剂购自青岛德慧精细化工有限公司。 实施例 1
本实施例用于说明本发明的彩色硅砂及其制备方法。
将 100kg硅砂加入到混砂机中, 在 100r/min的搅拌速度下, 冷却至 150 °C时, 加入 5kg环氧树脂 (型号为 E51 , 环氧值为 0.48-0.54eq/100g), 继续 搅拌, 得到环氧树脂与硅砂的均匀混合物。 然后, 在 100°C的温度下, 向混 合物中添加 0.2kg CR-826型钛白粉,搅拌 60s后,加入 1kg甲阶酚醛树脂(型 号为 2127), 继续搅拌 300s, 即得彩色硅砂。 经测定彩色硅砂的彩色树脂层 的平均厚度为 5 μηι。
对比例 1
按照实施例 1的方法的方法制备彩色硅砂, 不同的是, 在彩色硅砂制备 过程中, 没有添加环氧树脂和甲阶酚醛树脂。 实施例 2
本实施例用于说明本发明的彩色硅砂及其制备方法。
将 100kg硅砂加入到马弗炉中, 在 800°C下焙烧 20min, 然后直接将焙 烧后的硅砂转移至混砂机中, 在 100r/min的搅拌速度下, 冷却至 150°C时, 加入 5kg环氧树脂 (型号为 E51, 环氧值为 0.48-0.54eq/100g), 继续搅拌, 得到环氧树脂和硅砂的均匀混合物。 然后, 在 100°C的温度下, 向混合物中 添加 0.2kg CR-826型钛白粉, 搅拌 60s后, 加入 lkg甲阶酚醛树脂(型号为 2127), 继续搅拌 300s, 即得彩色硅砂。 经测定彩色硅砂的彩色树脂层的平 均厚度为 5 μηι。
实施例 3
本实施例用于说明本发明的彩色硅砂及其制备方法。
将 100kg硅砂加入到马弗炉中, 在 1000°C下焙烧 1 min, 然后直接将焙 烧后的硅砂转移至混砂机中, 在 200r/min的搅拌速度下, 冷却至 200°C时, 加入 10kg环氧树脂粘合剂(型号为 E51 , 环氧值为 0.48-0.54eq/100g), 继续 搅拌, 得到环氧树脂和硅砂的均匀混合物。 然后, 在 200°C的温度下, 向混 合物中添加 0.01kg CR-826型钛白粉, 搅拌 10s后, 加入 5kg甲阶酚醛树脂
(型号为 2127), 继续搅拌 600后, 加入 lkg矿物油 (型号为: X11644 ) , 搅拌均匀, 即得彩色硅砂。 经测定彩色硅砂的彩色树脂层的平均厚度为 10
实施例 4
本实施例用于说明本发明的彩色硅砂及其制备方法。
将 100kg硅砂加入到马弗炉中, 在 250°C下焙烧 60min, 然后直接将焙 烧后的硅砂转移至混砂机中, 在 50r/min的搅拌速度下, 冷却至 100°C时, 加入 0.01kg环氧树脂粘合剂 (型号为 E51 , 环氧值为 0.48-0.54eq/100g), 继 续搅拌, 得到环氧树脂和硅砂的均匀混合物。 然后, 在 50°C的温度下, 向混 合物中添加 0.5kg CR-826型钛白粉, 搅拌 30s后, 加入 0.001kg甲阶酚醛树 脂(型号为 2127),继续搅拌 100s后,加入 0.0001kg矿物油(型号为:X11644), 搅拌均匀, 即得彩色硅砂。 经测定彩色硅砂的彩色树脂层的平均厚度为 0.01
实施例 5
本实施例用于说明本发明的彩色硅砂及其制备方法。
将 100kg硅砂加入到马弗炉中, 在 600°C下焙烧 30min, 然后直接将焙 烧后的硅砂转移至混砂机中, 在 120r/min的搅拌速度下, 冷却至 160 °C时, 加入 lkg环氧树脂粘合剂 (型号为 E51 , 环氧值为 0.48-0.54eq/100g), 继续 搅拌, 得到环氧树脂和硅砂的均匀混合物。 然后, 在 120°C的温度下, 向其 中添加 0.2kg H190型炭黑, 搅拌 100s后, 加入 0.1kg甲阶酚醛树脂 (型号 为 2127), 继续搅拌 480后, 加入 0.1kg矿物油 (型号为: X11644) , 搅拌均 匀, 彩色硅砂。 经测定彩色硅砂的彩色树脂层的平均厚度为 1 μηι。 实施例 6
本实施例用于说明本发明的彩色硅砂及其制备方法。
将 100kg硅砂加入到马弗炉中, 在 400°C下焙烧 25min, 然后直接将焙 烧后的硅砂转移至混砂机中, 在 80r/min的搅拌速度下, 冷却至 120°C时, 加入 6kg环氧树脂粘合剂 (型号为 E51 , 环氧值为 0.48-0.54eq/100g), 继续 搅拌, 得到环氧树脂和硅砂的均匀混合物。然后, 在 80°C的温度下, 向其中 添加 0.2kg 4920型酞青蓝,搅拌 60s后,加入 3kg甲阶酚醛树脂 (型号为 2127 ), 继续搅拌 180s后, 加入 0.6kg矿物油 (型号为: X11644) , 搅拌均匀, 彩色 硅砂。 经测定彩色硅砂的彩色树脂层的平均厚度为 6 μηι。 硅砂着色效果测试
1、 表观颜色观察 肉眼观察实施例 1-6以及对比例 1中得到的着色硅砂, 颜色均匀且无未 着色硅砂的情况表示为〇, 反之, 表示为 X。 测试结果如表 1所示。
2、 硅砂颜色耐候性试验
使用氙灯老化试验箱 (北京鸿达天矩试验设备有限公司, 型号为 SN-500 ) , 按照 GB/T1865-1997对实施例 1-6以及对比例 1中得到的着色硅 砂进行氙弧辐射试验, 测试着色硅砂的耐候性。
将测试后颜色无明显变化的的表示为〇, 颜色发生明显变化标记为 X。 测试结果如表 1所示。
表 1
Figure imgf000013_0001
从表 1中的测试结果可以看出,对比例 1所得到的彩色硅砂或者着色不 均匀, 或者经氙弧辐射试验后发生颜色变化等问题。 而通过本发明的彩色硅 砂的制备方法得到的彩色硅砂具有良好表观颜色和耐候性。说明本发明的彩 色硅砂具有良好的颜色长期稳定性, 另外, 本发明的彩色硅砂的制备方法简 单, 易于在工业上应用。 实施例 7
本实施例用于说明本发明的彩色硅砂及其制备方法。
颜料剂的制备:
将购自上海新艳颜料有限公司的铁黄粉(320目筛余物 0.5重量%) 148 和购自廊坊翔宇钛白粉制造有限公司的钛白粉(325目筛余物 0.05重量%) 86g充分混合, 即可得到颜料剂 (CI ) lOOgo
彩色硅砂的制备: ( 1 )硅砂表面预处理步骤: 将 100kg硅砂加入到马弗炉中, 在 800°C下 焙烧 20min, 然后直接将焙烧后的硅砂转移至混砂机中, 在 lOOr/min的搅拌 速度下, 冷却至 150 °C时, 加入 5kg 环氧树脂粘合剂 (E51 , 环氧值为 0.48-0.54eq/100g), 继续搅拌。
(2 ) 硅砂着色步骤: 在 100°C的温度下, 向步骤 (1 ) 中的硅砂中添加 0.2kg颜料剂 C1 , 搅拌 60s后, 加入 lkg甲阶酚醛树脂 (型号为 2127), 继 续搅拌 300s后, 加入 0.5kg矿物油(X11644型), 搅拌均匀, 即得彩色硅砂。 实施例 8
本实施例用于说明本发明的彩色硅砂及其制备方法。
颜料剂的制备:
按照实施例 7的方法制备颜料剂 (C2 ) , 不同的是颜料剂的组成如表 2 所示。
彩色硅砂的制备:
( 1 ) 硅砂表面预处理步骤: 将 100kg硅砂加入到马弗炉中, 在 1000°C 下焙烧 lmin, 然后直接将焙烧后的硅砂转移至混砂机中, 在 200r/min的搅 拌速度下, 冷却至 200°C时, 加入 10kg环氧树脂粘合剂(型号为 E51 , 环氧 值为 0.48-0.54eq/100g), 继续搅拌。
(2 )硅砂着色步骤:在 200 °C的温度下,向步骤(1 )中的硅砂添加 0.01kg 颜料剂 C2, 搅拌 10s后, 加入 5kg甲阶酚醛树脂(型号为 2127), 继续搅拌 600s后, 加入 lkg矿物油 (型号为: X11644) , 搅拌均匀, 即得彩色硅砂。 实施例 9
本实施例用于说明本发明的彩色硅砂及其制备方法。
颜料剂的制备: 按照实施例 7的方法制备颜料剂 (C3), 不同的是颜料剂的组成如表 2 所示。
彩色硅砂的制备:
(1)硅砂表面预处理步骤: 将 100kg硅砂加入到马弗炉中, 在 250°C下 焙烧 60min, 然后直接将焙烧后的硅砂转移至混砂机中, 在 50r/min的搅拌 速度下, 冷却至 100°C时, 加入 0.01kg环氧树脂粘合剂 (型号为 E51, 环氧 值为 0.48-0.54eq/100g), 继续搅拌。
(2)硅砂着色步骤:在 50°C的温度下, 向步骤(1)中的硅砂添加 0.5kg 颜料剂 C3, 搅拌 30s后, 加入 0.001kg甲阶酚醛树脂 (型号为 2127), 继续 搅拌 100s后, 加入 0.0001kg矿物油 (型号为: X11644), 搅拌均匀, 即得 彩色硅砂。 实施例 10
本实施例用于说明本发明的彩色硅砂及其制备方法。
颜料剂的制备:
按照实施例 7的方法制备颜料剂 (C4), 不同的是颜料剂的组成如表 2 所示。
彩色硅砂的制备:
(1)硅砂表面预处理步骤: 将 100kg硅砂加入到马弗炉中, 在 600°C下 焙烧 20min, 然后直接将焙烧后的硅砂转移至混砂机中, 在 120r/min的搅拌 速度下, 冷却至 160°C时, 加入 lkg环氧树脂粘合剂 (型号为 E51, 环氧值 为 0.48-0.54eq/100g), 继续搅拌。
(2)硅砂着色步骤:在 120°C的温度下, 向步骤(1)中的硅砂添加 0.2kg 颜料剂 C4, 搅拌 100s后, 加入 0.1kg甲阶酚醛树脂 (型号为 2127), 继续 搅拌 480后, 加入 0.1kg矿物油 (型号为: X11644), 搅拌均匀, 即得彩色 硅砂。 实施例 11
本实施例用于说明本发明的彩色硅砂及其制备方法。
颜料剂的制备:
按照实施例 7的方法制备颜料剂 (C5 ), 不同的是颜料剂的组成如表 2 所示。
彩色硅砂的制备:
( 1 )硅砂表面预处理步骤: 将 100kg硅砂加入到马弗炉中, 在 400°C下 焙烧 25min, 然后直接将焙烧后的硅砂转移至混砂机中, 在 80r/min的搅拌 速度下, 冷却至 120°C时, 加入 6kg环氧树脂粘合剂 (型号为 E51 , 环氧值 为 0.48-0.54eq/100g), 继续搅拌。
(2)硅砂着色步骤:在 80°C的温度下, 向步骤(1 )中的硅砂添加 0.2kg 颜料剂 C5, 搅拌 60s后, 加入 3kg甲阶酚醛树脂(型号为 2127), 继续搅拌 180s后, 加入 0.6kg矿物油 (型号为: XI 1644), 搅拌均匀, 即得彩色硅砂。 实施例 12
本实施例用于说明本发明的彩色硅砂及其制备方法。
颜料剂的制备:
按照实施例 7的方法制备颜料剂 (C6), 不同的是颜料剂的组成如表 2 所示。
彩色硅砂的制备:
( 1 )硅砂表面预处理步骤: 将 100kg硅砂加入到马弗炉中, 在 800°C下 焙烧 20min, 然后直接将焙烧后的硅砂转移至混砂机中, 在 lOOr/min的搅拌 速度下, 冷却至 150 °C时, 加入 5kg 环氧树脂粘合剂 (E51 , 环氧值为 0.48-0.54eq/100g) , 继续搅拌。
(2 ) 硅砂着色步骤: 在 100°C的温度下, 向步骤 (1 ) 中的硅砂中添加 0.2kg颜料剂 C6, 搅拌 60s后, 加入 lkg甲阶酚醛树脂 (型号为 2127), 继 续搅拌 300s后, 加入 0.5kg矿物油(X11644型), 搅拌均匀, 即得彩色硅砂。 实施例 13
本实施例用于说明本发明的彩色硅砂及其制备方法。
颜料剂的制备:
按照实施例 7的方法制备颜料剂 (C7 ) , 不同的是颜料剂的组成如表 2 所示。
彩色硅砂的制备:
( 1 )硅砂表面预处理步骤: 将 100kg硅砂加入到马弗炉中, 在 800°C下 焙烧 20min, 然后直接将焙烧后的硅砂转移至混砂机中, 在 lOOr/min的搅拌 速度下, 冷却至 150 °C时, 加入 5kg 环氧树脂粘合剂 (E51 , 环氧值为 0.48-0.54eq/100g), 继续搅拌。
(2 ) 硅砂着色步骤: 在 100°C的温度下, 向步骤 (1 ) 中的硅砂中添加 0.2kg颜料剂 C7, 搅拌 60s后, 加入 lkg甲阶酚醛树脂 (型号为 2127), 继 续搅拌 300s后, 加入 0.5kg矿物油(X11644型), 搅拌均匀, 即得彩色硅砂。 硅砂着色效果测试
1、 硅砂表观颜色观察
肉眼观察分别使用实施例 7-13 中得到的彩色硅砂, 颜色均匀且无未着 色硅砂的情况表示为〇, 反之, 表示为 X。 测试结果如表 3所示。
2、 硅砂颜色耐候性试验
使用氙灯老化试验箱 (北京鸿达天矩试验设备有限公司, 型号为 SN-500 ) ,按照 GB/T1865-1997对分别使用实施例 7-13中得到的彩色硅砂进 行氙弧辐射试验, 测试着色硅砂的耐候性。
将测试后颜色无明显变化的的表示为〇, 颜色发生明显变化标记为 X。 测试结果如表 3所示。 表 2
Figure imgf000018_0001
Figure imgf000018_0002
耐候性。 说明本发明的彩色硅砂具有良好的颜色长期稳定性, 并且, 本发明 的彩色硅砂的制备方法简单, 易于在工业上应用。

Claims

权利要求书
1、 一种彩色硅砂, 该彩色硅砂包括硅砂基材和包覆在硅砂基材表面的 彩色树脂层, 所述彩色树脂层是由一种混合物固化而成, 所述混合物含有颜 料剂、 树脂和固化剂。
2、 根据权利要求 1所述的彩色硅砂, 其中, 所述彩色树脂层的平均厚 度为 0.01-10 μηΐο
3、 根据权利要求 1所述的彩色硅砂, 其中, 所述树脂选自环氧树脂、 酚醛树脂和呋喃树脂中的至少一种。
4、 根据权利要求 3所述的彩色硅砂, 其中, 以硅砂基材的重量为基准, 所述树脂的用量为 0.01-10重量%。
5、 根据权利要求 3所述的彩色硅砂, 其中, 所述树脂的重均分子量为 300-10000。
6、 根据权利要求 1所述的彩色硅砂, 其中, 以硅砂基材的重量为基准, 所述固化剂的用量为 0.001-5重量%。
7、 根据权利要求 6所述的彩色硅砂, 其中, 所述固化剂为双氰胺、 己 二酸二酰肼、 酸酐、 多元酚、 聚硫醇、 甲阶酚醛树脂、 氨基树脂、 脂肪族多 胺、 脂环族多胺、 聚酰胺、 改性芳胺、 咪唑以及三氟化硼络合物中的至少一 种。
8、 根据权利要求 1所述的彩色硅砂, 其中, 所述固化的条件包括: 固 化温度为 50-200°C, 固化时间为 30-600s。
9、 根据权利要求 1-8 中任意一项所述的彩色硅砂, 其中, 以硅砂基材 的重量为基准, 颜料剂的用量为 0.01-0.5重量%。
10、 根据权利要求 9所述的彩色硅砂, 其中, 所述颜料剂含有铁黄粉和 钛白粉, 其中, 以铁黄粉和钛白粉的总重量为基准, 铁黄粉的含量为 1-99 重量%, 钛白粉的含量为 99-1重量%。
11、 根据权利要求 10所述的彩色硅砂, 其中, 铁黄粉和钛白粉的重量 比为 0.1-10。
12、 根据权利要求 10所述的彩色硅砂, 其中, 以铁黄粉和钛白粉的总 重量为基准, 铁黄粉的含量为 10-30重量%, 钛白粉的含量为 70-90重量%。
13、 根据权利要求 12所述的彩色硅砂, 其中, 以铁黄粉和钛白粉的总 重量为基准, 铁黄粉的含量为 14-15重量%, 钛白粉的含量为 85-86重量%。
14、 根据权利要求 10所述的彩色硅砂, 其中, 该颜料剂还含有光稳定 剂。
15、 根据权利要求 14所述的彩色硅砂, 其中, 以颜料剂的总重量为基 准, 光稳定剂的含量为 0.01-50重量%。
16、 根据权利要求 14或 15所述的彩色硅砂, 其中, 光稳定剂为 酮、 苯并三唑和受阻胺中的至少一种, 或者所述光稳定剂为猝灭剂和光屏蔽 剂中的至少一种。
17、 一种权利要求 1-16 中任意一项所述的彩色硅砂的制备方法, 其特 征在于, 该方法包括:
将硅砂基材在 100-200 °C下与树脂混合均匀, 然后使硅砂基材和树脂的 混合物与颜料剂和固化剂接触, 在硅砂基材表面形成彩色树脂层。
18、 根据权利要求 17所述的彩色硅砂的制备方法, 其中, 该方法还包 括将与树脂混合前的硅砂基材在 250-1000 °C下热处理 l-60min。
19、 根据权利要求 17所述的彩色硅砂的制备方法, 其中, 所述接触的 温度为 50-200°C, 接触的时间为 30-600s。
PCT/CN2010/079430 2010-05-31 2010-12-03 一种彩色硅砂及其制备方法 WO2011150637A1 (zh)

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