CN101642926B - Artificial stone with photocatalysis - Google Patents
Artificial stone with photocatalysis Download PDFInfo
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- CN101642926B CN101642926B CN2009101730142A CN200910173014A CN101642926B CN 101642926 B CN101642926 B CN 101642926B CN 2009101730142 A CN2009101730142 A CN 2009101730142A CN 200910173014 A CN200910173014 A CN 200910173014A CN 101642926 B CN101642926 B CN 101642926B
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Abstract
The invention relates to a preparation method of an artificial stone, in particular to a preparation method of an artificial quartz stone with noctilucent function. The artificial quartz stone comprises raw materials containing natural quartz sand, unsaturated resin, accelerator, coupling agent and curing agent, a defined amount of color paste, fluorescent powder and photocatalyst. The artificial stone of the invention has the functions of decoration and indication, has broad-spectrum antibacterial property, can degrade organic pollutants in ambient environment, can remove the waste gas such as nitric oxide and the like, etc.
Description
Technical field
The present invention relates to a kind of preparation method of artificial stone; Particularly a kind of preparation method who has the artificial quartz in lump of noctilucent function simultaneously, its raw material is made up of natural siliceous sand, unsaturated-resin, promoter, coupling agent and curing agent and an amount of mill base, fluorescent material.
Background technology
Artificial stone is with blocks of natural stone or stone flour and mixed with resin, solidifies a kind of new decorative material that the back forms.At present, disclosed multiple artificial stone kind on the market and in the correlation technique.
Chinese patent CN1453301A reported a kind of in the entity plane materiel artificial stone material whole method of mixing the noctilucence light-storing material, but have that hardness is not enough, kind is single, can not make floor tile, the incandescnet particle consumption is big, cost is too high defective.
Chinese invention patent application 200810214635.6 discloses a kind of artificial quartz in lump preparation technology; This technological material contains quartz 0～90%, silica flour 5～90%, fiber 1～25%, resin 0.1～20%, coupling agent 0.1～5%, curing agent 0.1～5%, cullet 0～70%, broken eyeglass 0～70%, pigment 0～5%, shell 0～5% and sheet metal 0～5%; Above-mentioned raw material after fully mixing, is cured at the vacuum condition of 10～200 degree and forms needed artificial stone.Its used quartz particle diameter of lay special stress on is 0.1～20 millimeter in this patent application, and used silica flour is 300～2000 orders, and its best solidification temperature is 15～30 degree, or 60～90 degree, or 120～150 degree.Owing to adopted bigger quartz particle of granularity and superfine little silica flour in the raw material, the resin use amount is increased in this technology, this will reduce the intensity of finished-product material; Owing to need to use superfine silica flour, the finished product manufacturing cost is improved on the other hand; And the quartz that two types of granularities differ greatly in the raw material and silica flour can produce in manufacture process and gather partially, and the intensity of finished-product material is produced more negative influence; Because it need add hot pressing in making, energy consumption is higher in its preparation process, and the yield rate of press-formed product is not high simultaneously, has limited the large-scale production of artificial quartz in lump.
Chinese invention patent application 200710029148.8 discloses a kind of artificial quartz in lump and manufacturing process thereof with marbling and color.Material component that this is technological and proportioning are quartzy 52%～78%, 120～2000 orders quartzy 17%～38% of 24～120 orders.Unsaturated-resin and attach the material 6～14%, pigment 0.01%～10% of all kinds.Technology of the present invention seems advantages of simple, but the disclosed quartzy consumption of its patent application obviously is not enough according to its used amount of resin of general knowledge of this area; On the other hand should technology still need use the superfine silica flour of larger amt, its cost can be than higher equally; Identical with the technology of aforementioned 200810214635.6 patent applications, this technology needs heating too in curing, and energy consumption can be than higher during it was made.
A certain amount of luminescent powder of doping is also arranged in the prior art in artificial stone, make it can be luminous, strengthen its decorative effect at night.
But artificial stone prepared in the above-mentioned prior art can adhere to dirt in its surface in use unavoidably, or by germ contamination.Disclose a kind of antibiotic artificial stone preparation technology for addressing this problem Chinese patent CN1762880A, this technological antibiotic artificial stone contains resin 35～38%, aluminum hydroxide particles 5～12%, aluminium hydroxide inserts 49～59%, antiseptic 0.3～1.3%, pigment 0.2～0.5%; Above-mentioned material is passed through: feed intake, stir, add curing agent, vacuumize, cast, vacuumize, processing steps such as heat cure, back curing, sand milling, water mill finally make the finished product artificial stone.The use amount of resin is bigger in this patent, and this will reduce the intensity of finished-product material; Stress simultaneously to add silver, zinc ion antiseptic,, reach antibacterial effect, use precious metal ion, the finished product manufacturing cost is improved as antiseptic through continuous release metal ions; And can die down gradually with its antibacterial effect of release of metal ion.
Summary of the invention
The present invention provide a kind of cost relatively low, need not be heating and curing, do not need compression moulding, have than high finished product rate, the artificial quartz in lump preparation methods of effects such as antibacterial environment protection is arranged simultaneously.
Preparation method with artificial stone of photocatalysis of the present invention, its raw material is made up of natural siliceous sand, unsaturated-resin, promoter, coupling agent and curing agent and an amount of mill base, wherein:
A. the basic proportioning of material is following:
Natural siliceous sand: 10～20 order 25-16 weight %
20～40 order 25-30 weight %
40～80 order 10-12 weight %
80～200 order 10-12 weight %
200 orders, 14.5 weight %
325 orders, 14.5 weight %
Mill base: 0.3 weight %
Unsaturated-resin: 14-16 weight %
Photochemical catalyst: 0.1～10 weight %
Promoter: be about 1% of unsaturated-resin weight
Curing agent: be about 1% of unsaturated-resin weight
B. unsaturated-resin, mill base and luminescent powder and photochemical catalyst are stirred, add quartz sand then, the addition sequence of quartz sand is that the order number is descending, all need stir after each the feeding in raw material; Add promoter and curing agent successively, stir rapidly, in the mould with above-mentioned mixture injection molding; And place vacuum drying oven, kept 8 minutes, behind the taking-up mould; The 12-20 order quartz sand particle that takes a morsel is sprinkling upon die surface, lets the making sheet raw material solidify voluntarily, is cured to voluntarily when touching no longer sticking hand with hand at it; Remove mould, treat product drying after, fixed thick, polishing.
Among the preparation method of the artificial stone with photocatalysis of the present invention, used photochemical catalyst is an active titanic dioxide, or the titanium dioxide that mixes of nitrogen.
Among the preparation method of the artificial stone with photocatalysis of the present invention, also has the luminescent powder of 5 weight % in the basic proportioning of its material.
Titanium dioxide (the TiO that nitrogen used in the present invention mixes
2-xN
y) preparation method has two kinds, a kind of method be with commercial titanium dioxide as raw material, compound nitrogenous source with 10 weight % is like hexamethylenetetramine (HMT) or urea (CO (NH
2)
2) etc., with carrying out the mechanical alloying prepared in reaction through high speed ball mill after the two mixing; Another kind method is that the concentration with 40 weight % is that 20% titanium trichloride solution is a raw material, the hexamethylenetetramine of 18 weight % (HMT) or urea (CO (NH
2)
2) wait and be that nitrogenous source, the water of 42 weight % or ethanol or methyl alcohol are solvent, the three is mixed the back adopt hydro-thermal method or solvent-thermal method under 190 ℃ of conditions, to make.
Artificial stone of the present invention have production cost relatively low, in its preparation process, need not be heating and curing, do not need compression moulding, product has than high finished product rate.Owing to added coupling agent, improved the bond strength between resin and quartz sand among the present invention, the promoter that adds has then been improved the curing rate of material.
In the artificial stone of the present invention because TiO arranged
2Type photochemical catalyst, therefore this artificial stone in use can degrade organic pollution in the surrounding environment, remove waste gas such as nitrogen oxide; In addition, TiO
2Photochemical catalyst has broad spectrum antibacterial under ultraviolet light, radiation of visible light; It not only can kill most of microbe; The endotoxin that can also decomposing bacteria produces, and, in the process of sterilization, realize automatically cleaning with the thorough mineralising of organic nutrition matrix that the residual body of bacterium and bacterium depend on for existence; In antibiotic process, only play catalytic action, self does not consume, and can forever use in theory, to the environment non-secondary pollution.
Artificial stone of the present invention is owing to containing luminescent powder and ultraviolet, visible light type photochemical catalyst in its material prescription simultaneously; Therefore it can be by day veiling glare such as absorption sunshine naturally, when dark surrounds, begin luminously, fluorescent lifetime can reach 6-12 hour; Have very high ornamental, indicative; The self-luminous effect of ability utilization itself when dark surrounds continues to keep photocatalytic activity simultaneously, continues to produce photocatalytic activity.
The specific embodiment
To combine the specific embodiment that the present invention is further described below:
Embodiment 1: the luminous wine glass guarantor makes the production technology of quartzite slate.With raw material gross weight 1kg is example.Proportioning raw materials is as shown in table 1
Proportioning raw materials among table 1 embodiment 1
Take by weighing mill base 3 grams respectively, luminescent powder 10 grams, photochemical catalyst 10 grams add them in 140 gram resins; Stir, add 120 grams, 325 purpose quartz sands again, fully stir; The quartz that adds other order numbers then according to the descending order of order number respectively, add quartz at every turn after, all need fully to stir; Add promoter and curing agent at last, make the making sheet raw material after stirring rapidly, be poured in the making sheet mould.Mould is sent into vacuum tank vacuumize, air pressure reaches-keeps during 0.1MPa about 8 minutes backs and takes out moulds when vacuumizing, and the material surface in mould sprinkles one deck 10-20 purpose quartz sand (can prevent bonding like this); Let the making sheet raw material solidify voluntarily; Be cured to voluntarily when touching no longer sticking hand at it, remove mould, maintained at normal temperatures 15 days with hand; At last, the fixed thick quartzite slate that promptly makes of polishing.
As stock white being changed to the mill base of other colors, other technologies are constant, just can make the synthetic quartz slabstone of polychrome.
Embodiment 2: containing the production technology of noctilucence particle synthetic quartz stone slab, is example with raw material gross weight 1kg.Proportioning raw materials is as shown in table 2.
Proportioning raw materials among table 2 embodiment 2
At first for making the operation of noctilucence particle: with unsaturated-resin 40g, light-accumulated luminous powder 25 grams, aluminium hydrate powder 30 grams, promoter 0.4 gram; Curing agent 0.4 gram fully stirs, and after mixing, pours in the mould; Mould is sent into vacuum tank vacuumize, reach in vacuum-keep 3～5 minutes outlets, room temperature held a period of time under the condition of 0.1MPa; It is solidified fully, carry out fragmentation, sub-sieve again, promptly make 20-40 purpose luminescent powder particle.Getting 30 gram 20-40 purpose luminescent powder particles and 250 restrains 20-40 purpose quartzs and mixes subsequent use; Other operation is identical with embodiment 1.
Embodiment 3: the sign of photocatalysis effect (is example to decompose the acetaldehyde effect).
The artificial stone that makes is polished into the sheet material of 10cm * 10cm * 1cm, measures its initial mass m earlier
1, putting into volume then is the airtight transparent vessel of 860ml, and injects the acetaldehyde solution of 1ml40%, absorption is 2 hours under dark surrounds, records board quality m
2, then reactor is placed under the sunlight and shone 1 hour, carry out light-catalyzed reaction, record board quality m
3, be reapposed over again at last and make it under noctilucence effect own, proceed light-catalyzed reaction 1 hour under the dark surrounds, record its quality m
4Can know that the acetaldehyde quality of sheet material sample absorption is (m
2-m
1), be (m by the acetaldehyde quality of photocatalysis Decomposition under the solar radiation
2-m
3), the acetaldehyde quality that under the noctilucence effect, continues to be decomposed is (m
3-m
4), be example with the sample of the photochemical catalyst that adds 0.6wt%, record the acetaldehyde quality under its various process, as shown in table 3.
Acetaldehyde quality among table 3 embodiment 3
| Sample | (m 2-m 1) | (m 2-m 3) | (m 3-m 4) |
| Contrast artificial stone (not adding photochemical catalyst) | 0.1609g | 0.0277g | -0.0064g |
| Luminous wine glass is protected artificial stone (photochemical catalyst of 0.6wt%) | 0.1528g | 0.0959g | 0.0327g |
Can know by top experimental data, in that the ability that has higher photocatalysis Decomposition pollutant under the effect of sunlight is arranged, in the environment of dark, utilize the noctilucence of self, still have photocatalytic activity preferably with the artificial quartz in lump of method of the present invention preparation.
Titanium dioxide (the TiO that nitrogen used in the present invention mixes
2-xN
y) one of preparation method is:
The nitrogenous source of the commercial titanium dioxide of 90 weight % and 10 weight % (HMT or CO (NH
2)
2), make carrying out the mechanical alloying reaction through high speed ball mill after the two mixing;
The another kind of method of the titanium dioxide that preparation nitrogen mixes is:
40 weight % titanium trichloride solutions (concentration is 20%) are raw material, the hexamethylenetetramine of 18 weight % (HMT) or urea (CO (NH
2)
2) wait and be nitrogenous source, the water of 42 weight % (or ethanol, methyl alcohol etc.) is solvent, the three is mixed the back adopt hydro-thermal method or solvent-thermal method under 190 ℃ of conditions, to make.
Claims (6)
1. preparation method with artificial stone of photocatalysis, its raw material is made up of natural siliceous sand, unsaturated-resin, promoter, coupling agent and curing agent and an amount of mill base, it is characterized in that:
A. the basic proportioning of material is following:
Natural siliceous sand: 10～20 orders, 190 weight portions
20～40 orders, 240 weight portions
40～80 orders, 120 weight portions
80～200 orders, 100 weight portions
200 orders, 60 weight portions
325 orders, 120 weight portions
Mill base: 3 weight portions
Unsaturated-resin: 140 weight portions
Photochemical catalyst: 10 weight portions
Promoter: 2 weight portions
Curing agent: 2 weight portions
Used photochemical catalyst is the titanium dioxide that active titanic dioxide or nitrogen mix;
B. unsaturated-resin, mill base and luminescent powder and photochemical catalyst are stirred, add quartz sand then, the addition sequence of quartz sand is that the order number is descending, all need stir after each the feeding in raw material; Add promoter and curing agent successively, stir rapidly, in the mould with above-mentioned mixture injection molding; And place vacuum drying oven, kept 8 minutes, behind the taking-up mould; The 12-20 order quartz sand particle that takes a morsel is sprinkling upon die surface, lets the making sheet raw material solidify voluntarily, is cured to voluntarily when touching no longer sticking hand with hand at it; Remove mould, treat product drying after, fixed thick, polishing.
2. the preparation method with artificial stone of photocatalysis according to claim 1 is characterized in that in the basic proportioning of material also having the luminescent powder of 5 weight %.
3. preparation method with artificial stone of photocatalysis, its raw material is made up of natural siliceous sand, unsaturated-resin, promoter, coupling agent and curing agent and an amount of mill base, it is characterized in that:
A. the basic proportioning of material is following:
Natural siliceous sand: 10～20 orders, 170 weight portions
20～40 orders, 230 weight portions
40～80 orders, 120 weight portions
80～200 orders, 100 weight portions
200 orders, 60 weight portions
325 orders, 110 weight portions
Mill base: 3 weight portions
Unsaturated-resin: 170 weight portions
Photochemical catalyst: 10 weight portions
Promoter: 2 weight portions
Curing agent: 2 weight portions
Used photochemical catalyst is the titanium dioxide that active titanic dioxide or nitrogen mix;
B. unsaturated-resin, mill base and luminescent powder and photochemical catalyst are stirred, add quartz sand then, the addition sequence of quartz sand is that the order number is descending, all need stir after each the feeding in raw material; Add promoter and curing agent successively, stir rapidly, in the mould with above-mentioned mixture injection molding; And place vacuum drying oven, kept 8 minutes, behind the taking-up mould; The 12-20 order quartz sand particle that takes a morsel is sprinkling upon die surface, lets the making sheet raw material solidify voluntarily, is cured to voluntarily when touching no longer sticking hand with hand at it; Remove mould, treat product drying after, fixed thick, polishing.
4. the preparation method with artificial stone of photocatalysis according to claim 3 is characterized in that in the basic proportioning of material also having the luminescent powder of 5 weight %.
5. the titanium dioxide process that employed nitrogen mixes among the preparation method of the described arbitrary artificial stone with photocatalysis of claim 1 to 4; It is characterized in that with commercial titanium dioxide as raw material compound hexamethylenetetramine (HMT) or urea (CO (NH with 10 weight %
2)
2), with carrying out the mechanical alloying prepared in reaction through high speed ball mill after the two mixing.
6. the titanium dioxide process that employed nitrogen mixes among the preparation method of the described arbitrary artificial stone with photocatalysis of claim 1 to 4; It is characterized in that concentration with 40 weight % is that 20% titanium trichloride solution is a raw material, the hexamethylenetetramine of 18 weight % (HMT) or urea (CO (NH
2)
2) be nitrogenous source, the water of 42 weight % or ethanol or methyl alcohol are solvent, the three is mixed the back adopt hydro-thermal method or solvent-thermal method under 190 ℃ of conditions, to make.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101730142A CN101642926B (en) | 2009-08-28 | 2009-08-28 | Artificial stone with photocatalysis |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101730142A CN101642926B (en) | 2009-08-28 | 2009-08-28 | Artificial stone with photocatalysis |
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| Publication Number | Publication Date |
|---|---|
| CN101642926A CN101642926A (en) | 2010-02-10 |
| CN101642926B true CN101642926B (en) | 2012-01-11 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109571729A (en) * | 2018-11-08 | 2019-04-05 | 湖北冠泰建材有限公司 | Synthetic quartz plate native texture analogy method |
| CN109571729B (en) * | 2018-11-08 | 2020-12-11 | 湖北冠泰建材有限公司 | Artificial quartz plate natural texture simulation method |
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