CN107555841A - A kind of preparation method of anti-aging artificial quartz stone plate - Google Patents
A kind of preparation method of anti-aging artificial quartz stone plate Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of anti-aging artificial quartz stone plate, comprise the following steps:(1)Each raw material is weighed by proportioning, wherein the percentage by weight of each raw material is as follows:Aggregate 85 90%, resin 8 10%, curing agent 0.4 1%, coupling agent 0.3 0.5%, colorant 0.2 1%, antiseptic 1 3%, ultra-violet absorber 0.1 0.3%;(2)Antiseptic is added in resin, is stirred under vacuum mixing;Then colorant, coupling agent, aggregate, ultra-violet absorber are added, is stirred under vacuum mixing;Curing agent is eventually adding, mixing is stirred under vacuum, obtains compound;(3)Compound is evenly laid out in template;(4)Shutter vibration is compressing;(5)After vibration is compressing, solidification for the first time is carried out successively and is solidified for the second time.The present invention is effectively improved the mechanical performances such as hardness, the toughness of synthetic quartz slabstone by the optimization to composition of raw materials, improvement, the mutual cooperation of different material, and the improvement to preparation technology, and antimicrbial power is strong, and antibacterial action is lasting.
Description
Technical field
The present invention relates to building decoration technology field, more particularly to a kind of system of anti-aging artificial quartz stone plate
Preparation Method.
Background technology
Artificial quartz in lump(Or Buddha's warrior attendant/hard rock)Cradle is cried when entering Chinese within 2005 and matches sharp stone in Spain,
After artificial quartz in lump is approved by increasing consumer, China in 2006 starts someone and researches and develops artificial quartz in lump, 2007
Year successively has many producers to be proposed domestic artificial quartz in lump.Artificial quartz in lump is as new Artificial construction material, moistureproof, anti-
Acid, spelling property etc. have the advantages of lithotome is incomparable.In natural stone resource increasingly exhausted today, artificial stone
Diamond stone is its best substitute.Meanwhile artificial quartz in lump can make raw material using discarded glass, thus while environmental protection
Resource reutilization is realized, these advantages allow artificial quartz in lump to turn into the upstart of architectural decoration, therefore, are widely used in
The public buildings such as hotel, dining room, bank, hospital, exhibition, laboratory and kitchen countertop, commode, kitchen and bath's metope, dining table, tea
The house decoration such as several, windowsill, door pocket field.
However, artificial quartz in lump of the prior art also has the shortcomings that its is intrinsic, such as(1)Artificial quartz in lump is when in use
The effect of its surface can be contaminated by bacterial unavoidably, but common artificial quartz in lump does not suppress or killed to bacterium;(2)People
Make in quartz production after unsaturated polyester (UP) and filler solidification, long-term use of aging, its colour changed into yellow, hair easily occur for product
The problems such as crisp, physical property and chemical property decline, is not solved further also.
The content of the invention
The defects of in order to make up prior art, the present invention provide a kind of preparation side of anti-aging artificial quartz stone plate
Method.
The technical problems to be solved by the invention are achieved by the following technical programs:
A kind of preparation method of anti-aging artificial quartz stone plate, comprises the following steps:
(1)Each raw material is weighed by proportioning, and it is separated;The percentage by weight of wherein each raw material is as follows:Aggregate 85-90%,
Resin 8-10%, curing agent 0.4-1%, coupling agent 0.3-0.5%, colorant 0.2-1%, antiseptic 1-3%, ultra-violet absorber
0.1-0.3%;The percentage by weight sum of each component is 100%;The aggregate is made up of granular filler and powder filler, particle
The percentage by weight of filler is 20-30%, and the percentage by weight of powder filler is:70-80%;The granular filler is particle size
For the glass particle and quartz sand particle of 5-60 mesh, the ratio of weight and number of glass particle and quartz sand particle is 3:2;The powder
Last filler is the silica flour and bentonite that particle size is 160-1200 mesh, and its ratio of weight and number is 1:3;
(2)Antiseptic is added in resin, is stirred under vacuum 6~10min of mixing;Then add colorant, coupling agent, aggregate,
Ultra-violet absorber, it is stirred under vacuum 6~8min of mixing;Curing agent is eventually adding, 6~8min of mixing is stirred under vacuum, is mixed
Material;
(3)Compound is evenly laid out in template;
(4)Template is sent into vacuum vibration formation pressing machine and vibrates compressing, the vacuum in the vacuum vibration formation pressing machine
Degree control be -0.1~-0.08MPa, and the control of vacuum vibration formation pressing machine working frequency is 50Hz, and the static pressure on pressure head controls
For 30~50kg, 180~300s is suppressed;
(5)After vibration is compressing, solidification for the first time being carried out successively and is solidified for the second time, the temperature of the first time solidification is
70~90 DEG C, 15~20 minutes time;Second of 120 ± 2 DEG C of solidification temperature, hardening time are 10~30 minutes.
(6)After the completion of solidification, the room temperature completely rear sheet material thicknessing machine that enters to be cooled is fixed thick, then is set by water mill polishing
It is standby to be polished.
Material is successively added in the present invention and carries out vacuum stirring mixing, it is therefore intended that is eliminated that may be present in compound
Bubble, the finished product material that so manufactures is finer and closely woven, intensity is higher, surface is more bright and clean attractive in appearance.
Solidified at twice in the present invention, in order to ensure that curing reaction is steadily carried out, solidification safety, avoid anti-
Should be too fierce, produce stomata and waste material.
Further, the resin is made up of the composition of following percentage by weight:Polymethyl methacrylate 38%, phenolic aldehyde
Resin 46%, polybutadiene 16%.
Because quartz crystal relies primarily on resin-bonded, therefore, the quality of resin determines the quality of artificial quartz in lump.Mesh
Before, the artificial quartz in lump resin of in the market mainly uses unsaturated polyester resin, but unsaturated polyester resin is long-term use of to be held
The problems such as aging, its colour changed into yellow, embrittlement, physical property and chemical property decline easily occurs.The present invention is carried out to the composition of resin
Improve, found by numerous studies, this hair is used as using polymethyl methacrylate, phenolic resin, polybutadiene compounding
Bright resin, and the consumption proportion of Reasonable Regulation And Control each component, can overcome disadvantages mentioned above, make the artificial quartz in lump produced not
It is easy to aging.
Further, the coupling agent is γ-methacryloxypropyl trimethoxy silane, γ-(2,3- epoxies third
Oxygen) propyl trimethoxy silicane, N- β (aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N- (β-aminoethyl)-γ-ammonia
Propyl-triethoxysilicane, N- β (aminoethyl)-γ-aminopropyltrimethoxysilane, anilinomethyl triethoxysilane, γ-
Aminopropyl triethoxysilane, VTES, vinyltrimethoxy silane and γ-chloropropyl triethoxy
One kind in silane.
Further, the curing agent is peroxidating (2 ethyl hexanoic acid) tert-butyl ester, methyl ethyl ketone peroxide, benzoyl peroxide first
One kind in tert-butyl acrylate, dibenzoyl peroxide and fat polyamine.
Further, the ultra-violet absorber is phenyl salicylate, acetylsalicylic acid, benzene well triazole, 2- hydroxyl hexichol
At least one of ketone.
Further, the antiseptic is using the homogeneous mixture of modified zeolite and crude tourmaline as complex carrier,
The nano titanium oxide of selenium nitrogen tungsten codope is loaded on complex carrier, in described complex carrier, modified zeolite and it is natural electrically
The weight ratio of stone is(2-3)∶1.
Further, the preparation method of the antiseptic is:
(1)Isopropyl titanate, isopropanol and triethanolamine are mixed and stirred for 1.5-2 hours and obtain the first solution, wherein metatitanic acid
Isopropyl ester, isopropanol, the volume ratio of triethanolamine are 1:(5-6):0.8;
(2)Selenium powder and oxalic acid are added in deionized water, are uniformly mixing to obtain the second solution, wherein, mole of selenium powder and oxalic acid
Than for 1:3, the mol ratio of selenium powder and isopropyl titanate is 1:15;
(3)Urea and citric acid are added in deionized water, are uniformly mixing to obtain the 3rd solution, wherein, urea and citric acid
Mol ratio is 1:1.5, the mol ratio of urea and isopropyl titanate is 1:20;
(4)Ammonium tungstate and pyrolkigneous liquid are added in deionized water, obtain the 4th solution, wherein, mole of ammonium tungstate and pyrolkigneous liquid
Than for 1:2, the mol ratio of ammonium tungstate and isopropyl titanate is 1:30;
(5)Second solution, the 3rd solution and the 4th solution are mixed into the 4th solution, wherein the volume of the 4th solution is 30ml;
(6)By modified zeolite and crude tourmaline by weight(2-3):1 mixing, then ultra-fine grinding to average grain diameter are less than 5.0 μ
M, obtain complex carrier;
(7)In the presence of ultrasonic wave, the 4th solution is added dropwise in above-mentioned first solution, adds above-mentioned complex carrier,
Continue stir 1-3 hours obtain colloidal sol;
(8)It is put into after obtained colloidal sol is placed into ageing 2~3 days in Muffle furnace, 190 is warming up to 5~10 DEG C/minute of programming rates
~200 DEG C are incubated 3.5~4 hours, then are warming up to 550~580 DEG C of 40~50min of insulation with 12~15 DEG C/heating rate, with stove
It is cooled to and takes out cooling to be at room temperature ground to particle diameter be 200~400nm.
Further, the preparation method of the modified zeolite is:Stellerite ore is eluriated, crushing and processing to 560-
580 mesh;It is acidified using 1g epidesmine 0.1M hydrochloric acid 40ml as ratio, by the epidesmine and 15% sodium chloride after acidifying
Stirring reaction 3 hours under insulation, place 2 hours, washed to neutrality at room temperature, modified zeolite is obtained after drying.Using above-mentioned side
The modified zeolite that method obtains can partial removal zeolitic frameworks aluminium and the deposit that removes in duct form continuous empty passage,
Increase Zeolite and specific surface area, increase substantially its absorption property and heat endurance.Antiseptic is used as using modified zeolite
Carrier, the titanium dioxide of selenium nitrogen tungsten codope is efficiently distributed.
Titanium dioxide has two kinds of crystal formations of anatase titanium dioxide and rutile-type.With chemical property is stable, nontoxic, non-stimulated, Qiang Ping
The features such as covering ultraviolet.Titanium dioxide can not only influence bacterial reproduction power, moreover it is possible to destroy the membrane structure of bacterium, reach thorough
The purpose of bacterium for degrading.Nano titanium oxide belongs to non-dissolving type material, while degradable organic pollutant and killing bacterium, from
Body does not decompose, not dissolution, and photocatalysis is lasting, and with lasting sterilization, degradation of contaminant effect.The present invention uses selenium nitrogen
The nano titanium oxide of tungsten codope, compared with undoped nano titanium oxide, due to selenium, nitrogen, tungsten synergy, make
The band gap of titanium dioxide becomes narrower, therefore the response enhancing to visible ray, and suppresses the compound of electron-hole, simultaneously
Lattice defect is formd, advantageously forms more Ti3+Oxidation center so that its bactericidal property significantly improves.
Natural antibacterial agent pyrolkigneous liquid is with the addition of in the present invention, pyrolkigneous liquid can be attracted in the empty passage of modified zeolite,
More permanent antibacterial activity can be provided, there is the advantages of safety, green.
The nano titanium dioxide powder of selenium nitrogen tungsten codope is asked in application in the presence of what easy reunion, hardly possible were disperseed in the present invention
Topic, and drawbacks described above can be overcome by being carried on above-mentioned complex carrier.
Titanium dioxide is under light action in the present invention, and being activated produces the hole of electronegative electronics and positively charged and be
Row reaction, forms hole-electron pair, hydroxyl and the oxygen molecule capture that these both hole and electrons are adsorbed by titanium dioxide surface, generation
Hydroxyl radical free radical and superoxide anion radical, newly-generated free radical contact bacterium, they with bacterial cell in group
Reacted into composition, kill bacterium and play a part of antibacterial, and titanium dioxide in itself will not dissolution and decomposition, play and persistently kill
The effect of bacterium.But above-mentioned reaction needs a certain amount of hydrone, and the modified zeolite and crude tourmaline in the present invention can be with
Sufficient hydrone is provided, promotes the sterilization of titanium dioxide.
The nano titanium oxide of selenium nitrogen tungsten codope can preferably absorb the energy in sunshine in the present invention, there is provided give
Tourmaline, the anion releasability of tourmaline is improved, it is that have to the tourmaline in complex carrier in terms of antibacterial efficacy
The component of humidification, both have synergistic function, and antimicrbial power is strong, and antibacterial action is lasting.
The present invention has the advantages that:
The present invention by the optimization to composition of raw materials, improvement, the mutual cooperation of different material, and the improvement to preparation technology,
The mechanical performances such as hardness, the toughness of synthetic quartz slabstone are effectively improved, and antimicrbial power is strong, antibacterial action is lasting, improves
The combination property of synthetic quartz slabstone.
The present invention compounds the resin as the present invention using polymethyl methacrylate, phenolic resin, polybutadiene,
And the consumption proportion of Reasonable Regulation And Control each component, while ultra-violet absorber is with the addition of, there is the artificial quartz stone plate good
Ageing resistace.
Embodiment
With reference to embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It is not limitation of the invention.
Embodiment 1
A kind of anti-aging artificial quartz stone plate, it is made up of the raw material of following percentage by weight:Aggregate 87%, resin 9%,
Curing agent 0.7%, coupling agent 0.4%, colorant 0.7%, antiseptic 2%, ultra-violet absorber 0.2%;The weight percent of each component
It is 100% than sum;The aggregate is made up of granular filler and powder filler, and the percentage by weight of granular filler is 24%, powder
The percentage by weight of filler is:76%;The granular filler is the glass particle and quartz sand particle that particle size is 5-60 mesh,
The ratio of weight and number of glass particle and quartz sand particle is 3:2;The powder filler is the stone that particle size is 160-1200 mesh
English powder and bentonite, its ratio of weight and number are 1:3.
The resin is made up of the composition of following percentage by weight:Polymethyl methacrylate 38%, phenolic resin 46%, polybutadiene
Olefine resin 16%.
The coupling agent is γ-chloropropyl triethoxysilane;The curing agent is dibenzoyl peroxide;It is described ultraviolet
Light absorbers are phenyl salicylate.
The preparation method of the antiseptic is:
(1)Isopropyl titanate, isopropanol and triethanolamine are mixed and stirred for 1.5-2 hours and obtain the first solution, wherein metatitanic acid
Isopropyl ester, isopropanol, the volume ratio of triethanolamine are 1:5:0.8;
(2)Selenium powder and oxalic acid are added in deionized water, are uniformly mixing to obtain the second solution, wherein, mole of selenium powder and oxalic acid
Than for 1:3, the mol ratio of selenium powder and isopropyl titanate is 1:15;
(3)Urea and citric acid are added in deionized water, are uniformly mixing to obtain the 3rd solution, wherein, urea and citric acid
Mol ratio is 1:1.5, the mol ratio of urea and isopropyl titanate is 1:20;
(4)Ammonium tungstate and pyrolkigneous liquid are added in deionized water, obtain the 4th solution, wherein, mole of ammonium tungstate and pyrolkigneous liquid
Than for 1:2, the mol ratio of ammonium tungstate and isopropyl titanate is 1:30;
(5)Second solution, the 3rd solution and the 4th solution are mixed into the 4th solution, wherein the volume of the 4th solution is 30ml;
(6)By modified zeolite and crude tourmaline by weight 2:1 mixing, then ultra-fine grinding to average grain diameter are less than 5.0 μm, obtain
To complex carrier;The preparation method of wherein described modified zeolite is:Stellerite ore is eluriated, crushing and processing to 560-
580 mesh;It is acidified using 1g epidesmine 0.1M hydrochloric acid 40ml as ratio, by the epidesmine and 15% sodium chloride after acidifying
Stirring reaction 3 hours under insulation, place 2 hours, washed to neutrality at room temperature, modified zeolite is obtained after drying;
(7)In the presence of ultrasonic wave, the 4th solution is added dropwise in above-mentioned first solution, adds above-mentioned complex carrier,
Continue stir 1-3 hours obtain colloidal sol;
(8)It is put into after obtained colloidal sol is placed into ageing 2~3 days in Muffle furnace, 190 is warming up to 5~10 DEG C/minute of programming rates
~200 DEG C are incubated 3.5~4 hours, then are warming up to 550~580 DEG C of 40~50min of insulation with 12~15 DEG C/heating rate, with stove
It is cooled to and takes out cooling to be at room temperature ground to particle diameter be 200~400nm.
The preparation method of above-mentioned quartzite slate is:
(1)Each raw material is weighed by proportioning, and it is separated;
(2)Antiseptic is added in resin, is stirred under vacuum 6~10min of mixing;Then add colorant, coupling agent, aggregate,
Ultra-violet absorber, it is stirred under vacuum 6~8min of mixing;Curing agent is eventually adding, 6~8min of mixing is stirred under vacuum, is mixed
Material;
(3)Compound is evenly laid out in template;
(4)Template is sent into vacuum vibration formation pressing machine and vibrates compressing, the vacuum in the vacuum vibration formation pressing machine
Degree control be -0.1~-0.08MPa, and the control of vacuum vibration formation pressing machine working frequency is 50Hz, and the static pressure on pressure head controls
For 30~50kg, 180~300s is suppressed;
(5)After vibration is compressing, solidification for the first time being carried out successively and is solidified for the second time, the temperature of the first time solidification is
70~90 DEG C, 15~20 minutes time;Second of 120 ± 2 DEG C of solidification temperature, hardening time are 10~30 minutes.
(6)After the completion of solidification, the room temperature completely rear sheet material thicknessing machine that enters to be cooled is fixed thick, then is set by water mill polishing
It is standby to be polished.
Embodiment 2
A kind of anti-aging artificial quartz stone plate, it is made up of the raw material of following percentage by weight:Aggregate 85%, resin 10%,
Curing agent 0.4%, coupling agent 0.5%, colorant 1%, antiseptic 3%, ultra-violet absorber 0.1%;The percentage by weight of each component
Sum is 100%;The aggregate is made up of granular filler and powder filler, and the percentage by weight of granular filler is 20%, and powder is filled out
The percentage by weight of material is 80%;The granular filler is the glass particle and quartz sand particle that particle size is 5-60 mesh, glass
The ratio of weight and number of particle and quartz sand particle is 3:2;The powder filler is the silica flour that particle size is 160-1200 mesh
And bentonite, its ratio of weight and number are 1:3.
The resin is made up of the composition of following percentage by weight:Polymethyl methacrylate 38%, phenolic resin 46%, polybutadiene
Olefine resin 16%.
The coupling agent is vinyltrimethoxy silane;The curing agent is peroxidating (2 ethyl hexanoic acid) tert-butyl ester;
The ultra-violet absorber is acetylsalicylic acid.
The preparation method of the antiseptic is:
(1)Isopropyl titanate, isopropanol and triethanolamine are mixed and stirred for 1.5-2 hours and obtain the first solution, wherein metatitanic acid
Isopropyl ester, isopropanol, the volume ratio of triethanolamine are 1:6:0.8;
(2)Selenium powder and oxalic acid are added in deionized water, are uniformly mixing to obtain the second solution, wherein, mole of selenium powder and oxalic acid
Than for 1:3, the mol ratio of selenium powder and isopropyl titanate is 1:15;
(3)Urea and citric acid are added in deionized water, are uniformly mixing to obtain the 3rd solution, wherein, urea and citric acid
Mol ratio is 1:1.5, the mol ratio of urea and isopropyl titanate is 1:20;
(4)Ammonium tungstate and pyrolkigneous liquid are added in deionized water, obtain the 4th solution, wherein, mole of ammonium tungstate and pyrolkigneous liquid
Than for 1:2, the mol ratio of ammonium tungstate and isopropyl titanate is 1:30;
(5)Second solution, the 3rd solution and the 4th solution are mixed into the 4th solution, wherein the volume of the 4th solution is 30ml;
(6)By modified zeolite and crude tourmaline by weight 3:1 mixing, then ultra-fine grinding to average grain diameter are less than 5.0 μm, obtain
To complex carrier;The preparation method of wherein described modified zeolite is:Stellerite ore is eluriated, crushing and processing to 560-
580 mesh;It is acidified using 1g epidesmine 0.1M hydrochloric acid 40ml as ratio, by the epidesmine and 15% sodium chloride after acidifying
Stirring reaction 3 hours under insulation, place 2 hours, washed to neutrality at room temperature, modified zeolite is obtained after drying;
(7)In the presence of ultrasonic wave, the 4th solution is added dropwise in above-mentioned first solution, adds above-mentioned complex carrier,
Continue stir 1-3 hours obtain colloidal sol;
(8)It is put into after obtained colloidal sol is placed into ageing 2~3 days in Muffle furnace, 190 is warming up to 5~10 DEG C/minute of programming rates
~200 DEG C are incubated 3.5~4 hours, then are warming up to 550~580 DEG C of 40~50min of insulation with 12~15 DEG C/heating rate, with stove
It is cooled to and takes out cooling to be at room temperature ground to particle diameter be 200~400nm.
The preparation method of above-mentioned quartzite slate is:
(1)Each raw material is weighed by proportioning, and it is separated;
(2)Antiseptic is added in resin, is stirred under vacuum 6~10min of mixing;Then add colorant, coupling agent, aggregate,
Ultra-violet absorber, it is stirred under vacuum 6~8min of mixing;Curing agent is eventually adding, 6~8min of mixing is stirred under vacuum, is mixed
Material;
(3)Compound is evenly laid out in template;
(4)Template is sent into vacuum vibration formation pressing machine and vibrates compressing, the vacuum in the vacuum vibration formation pressing machine
Degree control be -0.1~-0.08MPa, and the control of vacuum vibration formation pressing machine working frequency is 50Hz, and the static pressure on pressure head controls
For 30~50kg, 180~300s is suppressed;
(5)After vibration is compressing, solidification for the first time being carried out successively and is solidified for the second time, the temperature of the first time solidification is
70~90 DEG C, 15~20 minutes time;Second of 120 ± 2 DEG C of solidification temperature, hardening time are 10~30 minutes.
(6)After the completion of solidification, the room temperature completely rear sheet material thicknessing machine that enters to be cooled is fixed thick, then is set by water mill polishing
It is standby to be polished.
Embodiment 3
A kind of anti-aging artificial quartz stone plate, it is made up of the raw material of following percentage by weight:Aggregate 90%, resin 8%,
Curing agent 0.4%, coupling agent 0.3%, colorant 0.2%, antiseptic 1%, ultra-violet absorber 0.1%;The weight percent of each component
It is 100% than sum;The aggregate is made up of granular filler and powder filler, and the percentage by weight of granular filler is 30%, powder
The percentage by weight of filler is 70%;The granular filler is the glass particle and quartz sand particle that particle size is 5-60 mesh, glass
The ratio of weight and number of glass particle and quartz sand particle is 3:2;The powder filler is the quartz that particle size is 160-1200 mesh
Powder and bentonite, its ratio of weight and number are 1:3.
The resin is made up of the composition of following percentage by weight:Polymethyl methacrylate 38%, phenolic resin 46%, polybutadiene
Olefine resin 16%.
The coupling agent is VTES;The curing agent is peroxidized t-butyl perbenzoate;The purple
Ultraviolet absorbers are benzene well triazole.
The preparation method of the antiseptic is:
(1)Isopropyl titanate, isopropanol and triethanolamine are mixed and stirred for 1.5-2 hours and obtain the first solution, wherein metatitanic acid
Isopropyl ester, isopropanol, the volume ratio of triethanolamine are 1:5:0.8;
(2)Selenium powder and oxalic acid are added in deionized water, are uniformly mixing to obtain the second solution, wherein, mole of selenium powder and oxalic acid
Than for 1:3, the mol ratio of selenium powder and isopropyl titanate is 1:15;
(3)Urea and citric acid are added in deionized water, are uniformly mixing to obtain the 3rd solution, wherein, urea and citric acid
Mol ratio is 1:1.5, the mol ratio of urea and isopropyl titanate is 1:20;
(4)Ammonium tungstate and pyrolkigneous liquid are added in deionized water, obtain the 4th solution, wherein, mole of ammonium tungstate and pyrolkigneous liquid
Than for 1:2, the mol ratio of ammonium tungstate and isopropyl titanate is 1:30;
(5)Second solution, the 3rd solution and the 4th solution are mixed into the 4th solution, wherein the volume of the 4th solution is 30ml;
(6)By modified zeolite and crude tourmaline by weight 2:1 mixing, then ultra-fine grinding to average grain diameter are less than 5.0 μm, obtain
To complex carrier;The preparation method of wherein described modified zeolite is:Stellerite ore is eluriated, crushing and processing to 560-
580 mesh;It is acidified using 1g epidesmine 0.1M hydrochloric acid 40ml as ratio, by the epidesmine and 15% sodium chloride after acidifying
Stirring reaction 3 hours under insulation, place 2 hours, washed to neutrality at room temperature, modified zeolite is obtained after drying;
(7)In the presence of ultrasonic wave, the 4th solution is added dropwise in above-mentioned first solution, adds above-mentioned complex carrier,
Continue stir 1-3 hours obtain colloidal sol;
(8)It is put into after obtained colloidal sol is placed into ageing 2~3 days in Muffle furnace, 190 is warming up to 5~10 DEG C/minute of programming rates
~200 DEG C are incubated 3.5~4 hours, then are warming up to 550~580 DEG C of 40~50min of insulation with 12~15 DEG C/heating rate, with stove
It is cooled to and takes out cooling to be at room temperature ground to particle diameter be 200~400nm.
The preparation method of above-mentioned quartzite slate is:
(1)Each raw material is weighed by proportioning, and it is separated;
(2)Antiseptic is added in resin, is stirred under vacuum 6~10min of mixing;Then add colorant, coupling agent, aggregate,
Ultra-violet absorber, it is stirred under vacuum 6~8min of mixing;Curing agent is eventually adding, 6~8min of mixing is stirred under vacuum, is mixed
Material;
(3)Compound is evenly laid out in template;
(4)Template is sent into vacuum vibration formation pressing machine and vibrates compressing, the vacuum in the vacuum vibration formation pressing machine
Degree control be -0.1~-0.08MPa, and the control of vacuum vibration formation pressing machine working frequency is 50Hz, and the static pressure on pressure head controls
For 30~50kg, 180~300s is suppressed;
(5)After vibration is compressing, solidification for the first time being carried out successively and is solidified for the second time, the temperature of the first time solidification is
70~90 DEG C, 15~20 minutes time;Second of 120 ± 2 DEG C of solidification temperature, hardening time are 10~30 minutes.
(6)After the completion of solidification, the room temperature completely rear sheet material thicknessing machine that enters to be cooled is fixed thick, then is set by water mill polishing
It is standby to be polished.
Comparative example 1
Based on embodiment 1, the difference is that only:Resin is unsaturated polyester resin in this comparative example.
Comparative example 2
Based on embodiment 1, the difference is that only:Resin is made up of the composition of following percentage by weight in this comparative example:Phenolic aldehyde
Resin 84%, polybutadiene 16%.
Comparative example 3
Based on embodiment 1, the difference is that only:Resin is made up of the composition of following percentage by weight in this comparative example:Poly- first
Base methyl acrylate 38%, polybutadiene 62%.
Comparative example 4
Based on embodiment 1, the difference is that only:Resin is made up of the composition of following percentage by weight in this comparative example:Poly- first
Base methyl acrylate 54%, phenolic resin 46%.
Comparative example 5
Based on embodiment 1, the difference is that only:Antiseptic is only used as carrier using modified zeolite in this comparative example.
Comparative example 6
Based on embodiment 1, the difference is that only:Antiseptic is only used as carrier using crude tourmaline in this comparative example.
Comparative example 7
Based on embodiment 1, the difference is that only:In this comparative example on complex carrier load undoped with nanometer titanium dioxide
Titanium.
Test example 1
Artificial quartz in lump obtained by 1-3 of the embodiment of the present invention and comparative example 1-4 is subjected to conventional products performance detection, the examination criteria
For:JC908-2013.
Mohs' hardness arranges from high to low:Embodiment 3>2=embodiment of embodiment 1>Comparative example 2>Comparative example 3>Comparative example 1>
Comparative example 4;Mohs' hardness wherein in embodiment 1 reaches 7, and the Mohs' hardness in comparative example 2 is 5.
Compression strength numerical value is higher, illustrates that the anti-pressure ability of sample is stronger, compression strength arranges from high to low:Embodiment 1>
Embodiment 3>Embodiment 2>Comparative example 2>Comparative example 4>Comparative example 1>Comparative example 3;Compression strength wherein in embodiment 2 is
356.5MPa, the compression strength in comparative example 2 is 172MPa.
Bending strength numerical value is higher, illustrates that the bending resistance of sample is stronger, bending strength arranges from high to low:Embodiment
1>Embodiment 3>Embodiment 2>Comparative example 4>Comparative example 2>Comparative example 3>Comparative example 1;Bending strength wherein in embodiment 2 is
82.2MPa, the bending strength in comparative example 4 is 41MPa.
Ball falling impact:In embodiment 1-3,225g steel balls are fallen from artificial quartz stone plate height fall 800mm,
The equal crack-free in surface and fragment;In comparative example 1-4,225g steel balls fall from artificial quartz stone plate height fall 800mm
Under, surface occurs rupturing and fragment.
Anti-aging test:After 200 hours degradations, outward appearance crack-free, bubble, slight crack and surface in embodiment 1-3
Texture changes, and has rupture, bubble, slight crack and surface tactile sensation change in comparative example 1-4;Color before and after burn-in test in embodiment 1-3
Difference is respectively 1.12,1.08,1.05, and aberration is respectively 1.5,1.6,1.5,1.4 before and after burn-in test in comparative example 1-4.
According to detection, 1-3 of embodiment of the present invention artificial quartz stone plate meets the standard, and relative to comparative example 1-
4, the physical detection performance of the artificial quartz stone plate of embodiment 1 to 3 is significantly increased, particularly compression strength, bending strength
Greatly enhanced with ball falling impact, and 1-3 of embodiment of the present invention ageing resistace is substantially better than comparative example 1-4.
Test example 2
Bacteriostatic experiment is carried out by the embodiment of the present invention 1 to 3 and with the artificial quartz in lump prepared by comparative example 5-7, experimental strain is
Staphylococcus aureus, inoculum density are 1.1 × 106Cfu/mL, by testing the logarithmic mean value after contacting elution 24 hours
Antilogarithm determine its fungistatic effect, the results showed that the antibacterial effect of the artificial quartz in lump of the embodiment of the present invention 1 to 3 is obvious
Better than comparative example 5-7.
Embodiment described above only expresses embodiments of the present invention, and its description is more specific and detailed, but can not
Therefore the limitation to the scope of the claims of the present invention is interpreted as, as long as the skill obtained using the form of equivalent substitution or equivalent transformation
Art scheme, it all should fall within the scope and spirit of the invention.
Claims (8)
1. a kind of preparation method of anti-aging artificial quartz stone plate, it is characterised in that comprise the following steps:
(1)Each raw material is weighed by proportioning, and it is separated;The percentage by weight of wherein each raw material is as follows:Aggregate 85-90%,
Resin 8-10%, curing agent 0.4-1%, coupling agent 0.3-0.5%, colorant 0.2-1%, antiseptic 1-3%, ultra-violet absorber
0.1-0.3%;The percentage by weight sum of each component is 100%;The aggregate is made up of granular filler and powder filler, particle
The percentage by weight of filler is 20-30%, and the percentage by weight of powder filler is:70-80%;The granular filler is particle size
For the glass particle and quartz sand particle of 5-60 mesh, the ratio of weight and number of glass particle and quartz sand particle is 3:2;The powder
Last filler is the silica flour and bentonite that particle size is 160-1200 mesh, and its ratio of weight and number is 1:3;
(2)Antiseptic is added in resin, is stirred under vacuum 6~10min of mixing;Then add colorant, coupling agent, aggregate,
Ultra-violet absorber, it is stirred under vacuum 6~8min of mixing;Curing agent is eventually adding, 6~8min of mixing is stirred under vacuum, is mixed
Material;
(3)Compound is evenly laid out in template;
(4)Template is sent into vacuum vibration formation pressing machine and vibrates compressing, the vacuum in the vacuum vibration formation pressing machine
Degree control be -0.1~-0.08MPa, and the control of vacuum vibration formation pressing machine working frequency is 50Hz, and the static pressure on pressure head controls
For 30~50kg, 180~300s is suppressed;
(5)After vibration is compressing, solidification for the first time being carried out successively and is solidified for the second time, the temperature of the first time solidification is
70~90 DEG C, 15~20 minutes time;Second of 120 ± 2 DEG C of solidification temperature, hardening time are 10~30 minutes;
(6)After the completion of solidification, the room temperature completely rear sheet material thicknessing machine that enters to be cooled is fixed thick, then enters by water mill polissoir
Row polishing.
2. the preparation method of artificial quartz stone plate as claimed in claim 1, it is characterised in that the resin is by following weight
The composition composition of percentage:Polymethyl methacrylate 38%, phenolic resin 46%, polybutadiene 16%.
3. the preparation method of artificial quartz stone plate as claimed in claim 1, it is characterised in that the coupling agent is γ-first
Base acryloxypropyl trimethoxy silane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, N- β (aminoethyl)-
γ-aminopropyltriethoxy dimethoxysilane, N- (β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N- β (aminoethyl)-γ-
Aminopropyl trimethoxysilane, anilinomethyl triethoxysilane, gamma-aminopropyl-triethoxy-silane, vinyl triethoxyl
One kind in silane, vinyltrimethoxy silane and γ-chloropropyl triethoxysilane.
4. the preparation method of artificial quartz stone plate as claimed in claim 1, it is characterised in that the curing agent is peroxidating
(2 ethyl hexanoic acid) tert-butyl ester, methyl ethyl ketone peroxide, peroxidized t-butyl perbenzoate, dibenzoyl peroxide and fat polyamine
In one kind.
5. the preparation method of artificial quartz stone plate as claimed in claim 1, it is characterised in that the ultra-violet absorber is
At least one of phenyl salicylate, acetylsalicylic acid, benzene well triazole, 2- hydroxy benzophenones.
6. the preparation method of artificial quartz stone plate as claimed in claim 1, it is characterised in that the antiseptic is boiled with modified
The homogeneous mixture of stone and crude tourmaline is as complex carrier, the nano-silica of load selenium nitrogen tungsten codope on complex carrier
Change titanium, in described complex carrier, the weight ratio of modified zeolite and crude tourmaline is(2-3)∶1.
7. the preparation method of artificial quartz stone plate as claimed in claim 6, it is characterised in that the preparation side of the antiseptic
Method is:
(1)Isopropyl titanate, isopropanol and triethanolamine are mixed and stirred for 1.5-2 hours and obtain the first solution, wherein metatitanic acid
Isopropyl ester, isopropanol, the volume ratio of triethanolamine are 1:(5-6):0.8;
(2)Selenium powder and oxalic acid are added in deionized water, are uniformly mixing to obtain the second solution, wherein, mole of selenium powder and oxalic acid
Than for 1:3, the mol ratio of selenium powder and isopropyl titanate is 1:15;
(3)Urea and citric acid are added in deionized water, are uniformly mixing to obtain the 3rd solution, wherein, urea and citric acid
Mol ratio is 1:1.5, the mol ratio of urea and isopropyl titanate is 1:20;
(4)Ammonium tungstate and pyrolkigneous liquid are added in deionized water, obtain the 4th solution, wherein, mole of ammonium tungstate and pyrolkigneous liquid
Than for 1:2, the mol ratio of ammonium tungstate and isopropyl titanate is 1:30;
(5)Second solution, the 3rd solution and the 4th solution are mixed into the 4th solution, wherein the volume of the 4th solution is 30ml;
(6)By modified zeolite and crude tourmaline by weight(2-3):1 mixing, then ultra-fine grinding to average grain diameter are less than 5.0 μ
M, obtain complex carrier;
(7)In the presence of ultrasonic wave, the 4th solution is added dropwise in above-mentioned first solution, adds above-mentioned complex carrier,
Continue stir 1-3 hours obtain colloidal sol;
(8)It is put into after obtained colloidal sol is placed into ageing 2~3 days in Muffle furnace, 190 is warming up to 5~10 DEG C/minute of programming rates
~200 DEG C are incubated 3.5~4 hours, then are warming up to 550~580 DEG C of 40~50min of insulation with 12~15 DEG C/heating rate, with stove
It is cooled to and takes out cooling to be at room temperature ground to particle diameter be 200~400nm.
8. the preparation method of artificial quartz stone plate as claimed in claim 6, it is characterised in that the preparation of the modified zeolite
Method is:Stellerite ore is eluriated, crushing and processing to 560-580 mesh;Using 1g epidesmines 0.1M hydrochloric acid 40ml as than
Example be acidified, by the epidesmine after acidifying and 15% sodium chloride under insulation stirring reaction 3 hours, place 2 at room temperature
Hour, wash to neutrality, modified zeolite is obtained after drying.
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