CN107128110B - Novel ink stone - Google Patents

Novel ink stone Download PDF

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Publication number
CN107128110B
CN107128110B CN201710270934.0A CN201710270934A CN107128110B CN 107128110 B CN107128110 B CN 107128110B CN 201710270934 A CN201710270934 A CN 201710270934A CN 107128110 B CN107128110 B CN 107128110B
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weight
parts
parent
raw material
inkstone
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CN107128110A (en
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胡秋生
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Ancient City Huangshan She Yan Co Ltd
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Ancient City Huangshan She Yan Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43L—ARTICLES FOR WRITING OR DRAWING UPON; WRITING OR DRAWING AIDS; ACCESSORIES FOR WRITING OR DRAWING
    • B43L27/00—Ink stands
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/18—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Structural Engineering (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention provides a kind of novel ink stone, including inkstone parent and the anticorrosion layer positioned at rub-down ink area and the light-absorption layer positioned at inkstone parent side wall.The inkstone is not susceptible to corrosion phenomenon, and intensity is high, will not lead to reduction in performance of ink, also, the novel ink stone can prevent prepared Chinese ink from solidifying.

Description

Novel ink stone
Technical field
The present invention relates to inkstone technical field more particularly to a kind of novel ink stones for storing ink and heating function.
Background technology
Inkstone is one of important class of the ancient Chinese tradition divine force that created the universe, the hat of the writing brush, ink stick, ink slab and paper, be collection it is aesthetic with it is practical be one The ancient Chinese art design of body.The needs that inkstone is born in, from with the art work that combination of appreciation and practicality is gradually evolved into for ancestor.In Among one inkstone, we, which can not only sample, enjoys the beautiful of material texture, carves intention, and the Seiko of artistic technique is exquisite, meanwhile, Inkstone is undoubtedly a posting of traditional Chinese culture, accumulation and epitome.
Traditional inkstone pass through the long period use, prepared Chinese ink generate corrosion under, inkstone is susceptible to crack, shape Into tiny hole, make inkstone strength reduction, crack makes ink permeation, causes to store performance of ink reduction.In addition, existing inkstone exists In the case that weather is colder, the prepared Chinese ink of grinding can turn cold, and solidification influences to use.
The present invention provides novel ink stone, which is not susceptible to corrosion phenomenon, and intensity is high, will not lead to drop in performance of ink It is low, also, the novel ink stone can prevent prepared Chinese ink from solidifying.
Invention content
The technical problems to be solved by the invention are to provide a kind of novel ink stone, which is not susceptible to corrosion phenomenon, by force Degree is high, will not lead to reduction in performance of ink, also, the novel ink stone can prevent prepared Chinese ink from solidifying.
In order to solve the above technical problems, the present invention provides a kind of novel ink stone, including inkstone parent and positioned at rub-down ink The anticorrosion layer in area and the light-absorption layer positioned at inkstone parent side wall.
The raw material for preparing the parent includes calcite, clay, quartz, silica modified unsaturated polyester (UP) and curing Agent.
The weight percent of each raw material is respectively calcite 3%~8%, clay 35%~40%, quartz 35% in the parent ~45%, silica modified unsaturated polyester (UP) 15%~20% and curing agent 1%~2%, the quality sum of each raw material is 100%.
The preparation method of the silica modified polyester includes：
The first step crushes silica, dries at high temperature, sieves with 100 mesh sieve, and often takes the silica after 300g sievings Powder adds in the aqueous solution 200ml (content of stearic acid sodium is 3g in 100ml solution) of surface modifier stearic acid sodium, in room The lower high-speed stirred of temperature 30 minutes, filtering, filter cake is washed 3 times with absolute ethyl alcohol, and each ethanol consumption is 30ml, and filtration cakes torrefaction is ground It clays into power；
Second step using 5g rutgers as measurement basis, often adds 5g terephthalic acid (TPA)s two in reaction vessel Methyl esters, addition 1,2-PD 10g, tetra-n-butyl titanate 1g, are passed through nitrogen, heat temperature raising treats that material melts in reaction vessel Start to stir after melting, controlling reaction temperature is in 180 degree, when acid value drops to 8mgKOH/g, reduces temperature, further adds in 30g Maleic anhydride, 1,2-PD 30g30g (based on 5g dimethyl terephthalate (DMT)s), continue esterification, control Reaction temperature processed stirs 2 hours~3 hours at 200 DEG C or so, is cooled to 90 DEG C, and insulated and stirred is uniformly to obtain the final product.
Third walks, and powder prepared by the 5g first steps is often taken to be added in the product of second step preparation and is sufficiently stirred, adds in and promotees It is mixed evenly into agent benzoyl peroxide 0.05g, is put into vacuum defoamation in vacuum drying chamber, after normal temperature cure for 24 hours, then risen Temperature is ground into powder to 90 DEG C of curing 2h.
Be used to form the corrosion resistance coating of the anticorrosion layer raw material include alkamine modified epoxy resin, silica, Water, pyrrolidones, acrylate and KH-560.
The weight of each raw material is respectively in the corrosion resistance coating, relative to the alkamine modified epoxy resin of 100 parts by weight, institute The dosage of silica is stated as the parts by weight of 40 parts by weight~50, the parts by weight of the pyrrolidones are the parts by weight of 5 parts by weight~8, The parts by weight of 20 parts by weight of acrylate~30, KH-560 are the parts by weight of 3 parts by weight~5, and in terms of solid, the dosage of the water is The parts by weight of 100 parts by weight~150.
The preparation method of the alkamine modified epoxy resin is that solvent absolute ethyl alcohol and bisphenol A-type are added in reaction vessel The molar ratio of epoxy resin, stirring preheating 50 minutes at 60 DEG C, solvent absolute ethyl alcohol and bisphenol A type epoxy resin is 4:1, with After be slowly added to diglycolamine, the molar ratio of diglycolamine and bisphenol A type epoxy resin is 0.3:1, it is small to be warming up to 85 DEG C of reactions 3 When, it is then cooled in 60 DEG C of addition glacial acetic acid and is neutralized into salt, the molar ratio of bisphenol A type epoxy resin and glacial acetic acid is 1:0.3 ~0.4, it reacts 40 minutes, adds in deionized water, obtain alkamine modified epoxy resin, bisphenol A type epoxy resin and deionized water Ratio correspond to 10ml deionized waters for 1mol resins.
The raw material for being used to form the light absorption paint of the light-absorption layer includes sulfonate modified carbon nanotube, diazo naphthoquinone chemical combination Object, novolac resin and ethyl lactate solvent.
The parts by weight of each raw material are respectively the weight of sulfonate modified 5 parts by weight of carbon nanotube~10 in the light absorption paint Part, the parts by weight of the parts by weight of 8 parts by weight of diazo naphthoquinone compound~12,50 parts by weight of novolac resin~60 and ethyl lactate it is molten The parts by weight of 30 parts by weight of agent~40.
The preparation method of the diazo naphthoquinone compound is in terms of 5g diazo naphthoquinone sulfonic acid chloride weight, by diazo naphthoquinone sulphonyl Chlorine 5g and trihydroxybenzophenone 2g is put into reaction vessel, is added in 50ml acetone stirring and dissolvings, is then added in 5ml water, slowly The triethylamine with trihydroxybenzophenone equimolar amounts is added dropwise, triethylamine is dissolved in acetone soln and is added dropwise, after being added dropwise extremely Reaction is completed, and reaction solution is stirred down and is poured into 300ml distilled water, is added in chloride solid and is dissolved, promotes reaction product It is precipitated, filtering is washed three times, in drying to perseverance, obtains solid.
The preparation method of the sulfonate modified carbon nanotube includes：
The first step, carbon nanotube is impregnated in concentrated sulfuric acid, ultrasonic disperse, the reflow treatment 1h at 90 DEG C, and suction filtration is used in combination Deionized water is washed till neutrality, freeze-drying；
The product of the first step is dissolved in water by second step, is added drop-wise in aminobenzenesulfonic acid diazonium salt solution, carbon nanotube Mass ratio with aminobenzenesulfonic acid diazol is 1:2, it reacts 5 hours in a water bath, then the reaction was continued at normal temperatures 3 hours, It filters after reaction, and is rinsed with deionized water, freeze-drying obtains product.
The present invention also provides the preparation method of above-mentioned inkstone, including：
Each raw material is added in blender and stirred evenly, is packed into mold, uniform compaction, at 30 DEG C~40 DEG C by the first step Curing 3 hours, obtains parent；
Second step is carved, and parent is engraved as to the pattern of various needs as needed；
Third walks, polishing, and black system is carried out to the parent after engraving, makes its smooth, smooth, removes unnecessary tool marks；
4th step, coating, in the rub-down ink area of parent, coating corrosion resistance coating forms anticorrosion layer, and light absorption paint shape is coated in side wall Into light-absorption layer.
Beneficial effects of the present invention:
Inkstone provided by the invention is not susceptible to corrosion phenomenon, and intensity is high, will not lead to reduction in performance of ink, also, should Novel ink stone can prevent prepared Chinese ink from solidifying.
Description of the drawings
The infrared spectrum of the alkamine modified epoxy resin of Fig. 1；
The infrared spectrum of the silica modified polyester of Fig. 2；
The infrared spectrum of the sulfonate modified carbon nanotubes of Fig. 3.
Specific embodiment
The present invention provides a kind of novel ink stone, including inkstone parent and positioned at the anticorrosion layer in rub-down ink area and positioned at inkstone The light-absorption layer of parent side wall.
The raw material for preparing the parent includes calcite, clay, quartz, silica modified unsaturated polyester (UP) and curing Agent.
Further preferably, the parent is only prepared by above-mentioned raw materials.
The weight percent of each raw material is respectively calcite 3%~8%, clay 35%~40%, quartz 35% in the parent ~45%, silica modified unsaturated polyester (UP) 15%~20% and curing agent 1%~2%, the quality sum of each raw material is 100%.
The weight of each raw material is further preferably respectively calcite 6%, clay 35%, quartz 40%, dioxy in the parent SiClx modified unsaturated polyester 18% and curing agent 1%.
The curing agent is methyl ethyl ketone peroxide.
The addition of silica modified polyester can enhance its toughness while inkstone hardness is kept, and reduce due to corrosion Inkstone hardness reduces caused by the crack that phenomenon generates, and reduces the possibility that inkstone crushes.The silica modified polyester Preparation method includes：
The first step crushes silica, dries at high temperature, sieves with 100 mesh sieve, and often takes the silica after 300g sievings Powder adds in the aqueous solution 200ml (content of stearic acid sodium is 3g in 100ml solution) of surface modifier stearic acid sodium, in room The lower high-speed stirred of temperature 30 minutes, filtering, filter cake is washed 3 times with absolute ethyl alcohol, and each ethanol consumption is 30ml, and filtration cakes torrefaction is ground It clays into power；
Second step using 5g rutgers as measurement basis, often adds 5g terephthalic acid (TPA)s two in reaction vessel Methyl esters, addition 1,2-PD 10g, tetra-n-butyl titanate 1g, are passed through nitrogen, heat temperature raising treats that material melts in reaction vessel Start to stir after melting, controlling reaction temperature is in 180 degree, when acid value drops to 8mgKOH/g, reduces temperature, further adds in 30g Maleic anhydride, 1,2-PD 30g30g (based on 5g dimethyl terephthalate (DMT)s), continue esterification, control Reaction temperature processed stirs 2 hours~3 hours at 200 DEG C or so, is cooled to 90 DEG C, and insulated and stirred is uniformly to obtain the final product.
Third walks, and powder prepared by the 5g first steps is often taken to be added in the product of second step preparation and is sufficiently stirred, adds in and promotees It is mixed evenly into agent benzoyl peroxide 0.05g, is put into vacuum defoamation in vacuum drying chamber, after normal temperature cure for 24 hours, then risen Temperature is ground into powder to 90 DEG C of curing 2h.
The present invention also provides the preparation method of above-mentioned inkstone, including：
Each raw material is added in blender and stirred evenly, is packed into mold, uniform compaction, at 30 DEG C~40 DEG C by the first step Curing 3 hours, obtains parent；
Second step is carved, and parent is engraved as to the pattern of various needs as needed；
Third walks, polishing, and black system is carried out to the parent after engraving, makes its smooth, smooth, removes unnecessary tool marks；
4th step, coating, in the rub-down ink area of parent, coating corrosion resistance coating forms anticorrosion layer, and light absorption paint shape is coated in side wall Into light-absorption layer.
The anticorrosion layer is to coat a floor corrosion resistance coating in rub-down ink area on the basis of inkstone parent to form, and anticorrosion layer is deposited Prepared Chinese ink is made not contacted easily with parent, so as to prevent corrosion generate crack caused by inkstone hardness reduce.
The raw material of the corrosion resistance coating includes alkamine modified epoxy resin, silica, water, pyrrolidones, acrylate And KH-560.
Further, the corrosion resistance coating is only prepared by above-mentioned raw materials.
The weight of each raw material is respectively in the corrosion resistance coating, relative to the alkamine modified epoxy resin of 100 parts by weight, institute The dosage of silica is stated as the parts by weight of 40 parts by weight~50, the parts by weight of the pyrrolidones are the parts by weight of 5 parts by weight~8, The parts by weight of 20 parts by weight of acrylate~30, KH-560 are the parts by weight of 3 parts by weight~5, and in terms of solid, the dosage of the water is The parts by weight of 100 parts by weight~150.
Further preferably, the weight of each raw material is respectively in the corrosion resistance coating, relative to the alkamine modified of 100 parts by weight Epoxy resin, the dosage of the silica are 50 parts by weight, and the parts by weight of the pyrrolidones are 6 parts by weight, acrylate 25 parts by weight, KH-560 is 4 parts by weight, and in terms of solid, the dosage of the water is 120 parts by weight.
The preparation method of the alkamine modified epoxy resin is that solvent absolute ethyl alcohol and bisphenol A-type are added in reaction vessel The molar ratio of epoxy resin, stirring preheating 50 minutes at 60 DEG C, solvent absolute ethyl alcohol and bisphenol A type epoxy resin is 4:1, with After be slowly added to diglycolamine, the molar ratio of diglycolamine and bisphenol A type epoxy resin is 0.3:1, it is small to be warming up to 85 DEG C of reactions 3 When, it is then cooled in 60 DEG C of addition glacial acetic acid and is neutralized into salt, the molar ratio of bisphenol A type epoxy resin and glacial acetic acid is 1:0.3 ~0.4, it reacts 40 minutes, adds in deionized water, obtain alkamine modified epoxy resin, bisphenol A type epoxy resin and deionized water Ratio correspond to 10ml deionized waters for 1mol resins.
The bisphenol A type epoxy resin is epoxy resin E51.
The present invention also provides the preparation methods of above-mentioned corrosion resistance coating, are specially blended in above-mentioned each raw material by weight Together, 30 DEG C~40 DEG C are heated to, is stirred 2~3 hours, is down to room temperature, obtains coating.
The light-absorption layer is to coat one layer of light absorption paint in side wall on the basis of inkstone parent to form, and the light-absorption layer leads to It crosses and luminous energy is converted to thermal energy, inkstone bulk temperature can be made higher, ensure that prepared Chinese ink is not easy to condense into solid, it is easy to use.
The raw material of the light absorption paint includes sulfonate modified carbon nanotube, diazo naphthoquinone compound, novolac resin With ethyl lactate solvent.
Further preferably, the light absorption paint is only prepared by above-mentioned raw materials.
The parts by weight of each raw material are respectively the weight of sulfonate modified 5 parts by weight of carbon nanotube~10 in the light absorption paint Part, the parts by weight of the parts by weight of 8 parts by weight of diazo naphthoquinone compound~12,50 parts by weight of novolac resin~60 and ethyl lactate it is molten The parts by weight of 30 parts by weight of agent~40.
Further preferably, the parts by weight of each raw material are respectively sulfonate modified 8 weight of carbon nanotube in the light absorption paint Part, 35 parts by weight of 10 parts by weight of diazo naphthoquinone compound, 55 parts by weight of novolac resin and ethyl lactate solvent.
The preparation method of the diazo naphthoquinone compound is in terms of 5g diazo naphthoquinone sulfonic acid chloride weight, by diazo naphthoquinone sulphonyl Chlorine 5g and trihydroxybenzophenone 2g is put into reaction vessel, is added in 50ml acetone stirring and dissolvings, is then added in 5ml water, slowly The triethylamine with trihydroxybenzophenone equimolar amounts is added dropwise, triethylamine is dissolved in acetone soln and is added dropwise, after being added dropwise extremely Reaction is completed, and reaction solution is stirred down and is poured into 300ml distilled water, is added in chloride solid and is dissolved, promotes reaction product It is precipitated, filtering is washed three times, in drying to perseverance, obtains solid.
The preparation method of the sulfonate modified carbon nanotube includes：
The first step, carbon nanotube is impregnated in concentrated sulfuric acid, ultrasonic disperse, the reflow treatment 1h at 90 DEG C, and suction filtration is used in combination Deionized water is washed till neutrality, freeze-drying；
The product of the first step is dissolved in water by second step, is added drop-wise in aminobenzenesulfonic acid diazonium salt solution, carbon nanotube Mass ratio with aminobenzenesulfonic acid diazol is 1:2, it reacts 5 hours in a water bath, then the reaction was continued at normal temperatures 3 hours, It filters after reaction, and is rinsed with deionized water, freeze-drying obtains product.
The concentrated sulfuric acid be commercial product, a concentration of 98%.
The present invention also provides the preparation methods of above-mentioned light absorption paint, are specially blended in above-mentioned each raw material by weight Together, 45 DEG C~60 DEG C are heated to, is stirred 1~2 hour, is down to room temperature, obtains coating.
The present invention will be described in detail below with reference to the drawings of preferred embodiments, whereby to the present invention how applied technology method To solve technical problem, and the realization process for reaching technique effect can fully understand and implement according to this.
1 alkamine modified epoxy resin of embodiment
Solvent absolute ethyl alcohol and bisphenol A type epoxy resin E51 are added in reaction vessel, the molar ratio of the two is 4:1, Stirring preheating 50 minutes at 60 DEG C are then slowly added to mole of diglycolamine, diglycolamine and bisphenol A type epoxy resin E51 Than being 0.3:1, it is warming up to 85 DEG C and reacts 3 hours, be then cooled in 60 DEG C of addition glacial acetic acid and be neutralized into salt, bisphenol type epoxy The molar ratio of resin E51 and glacial acetic acid is 1:0.3, it reacts 40 minutes, adds in deionized water, obtain alkamine modified epoxy resin, Bisphenol A type epoxy resin and the ratio of deionized water are the corresponding 10ml deionized waters of 1mol resins, obtain alkamine modified asphalt mixtures modified by epoxy resin Fat.
The infrared spectrum of product is shown in that Fig. 1, a are epoxy resin spectrogram before modified, and b is modified epoxy resin spectrogram.
2 silica modified polyester of embodiment
Silica is crushed, is dried at high temperature, is sieved with 100 mesh sieve, the SiO 2 powder after 300g sievings is often taken, adds Enter the aqueous solution 200ml (content of stearic acid sodium is 3g in 100ml solution) of surface modifier stearic acid sodium, at room temperature at a high speed Stirring 30 minutes, filtering, filter cake wash 3 times with absolute ethyl alcohol, and each ethanol consumption is 30ml, filtration cakes torrefaction, grind into powder, Using 5g rutgers as measurement basis, 5g dimethyl terephthalate (DMT)s, addition 1,2- third are often added in reaction vessel Glycol 10g, tetra-n-butyl titanate 1g are passed through nitrogen in reaction vessel, and heat temperature raising starts to stir after material melts, control Reaction temperature processed is in 180 degree, when acid value drops to 8mgKOH/g, reduces temperature, further adds in 30g maleic anhydrides, 1, 2- propylene glycol 30g30g (based on 5g dimethyl terephthalate (DMT)s), continues esterification, controlling reaction temperature is 200 DEG C or so, it stirs 2 hours~3 hours, is cooled to 90 DEG C, insulated and stirred uniformly to obtain the final product, often takes powder prepared by the 5g first steps to add Enter and be sufficiently stirred in the product prepared to second step, add in accelerating agent benzoyl peroxide 0.05g and be mixed evenly, be put into true Vacuum defoamation in empty drying box after normal temperature cure for 24 hours, then is warming up to 90 DEG C of curing 2h, is ground into powder, obtains silica and change Property polyester.
The infrared spectrum of product is shown in that Fig. 2, a are silica modified spectrogram, and b is polyester infrared spectrum, and c is product spectrogram.
3 diazo naphthoquinone compound of embodiment
In terms of 5g diazo naphthoquinone sulfonic acid chloride weight, diazo naphthoquinone sulfonic acid chloride 5g with trihydroxybenzophenone 2g is put into and is reacted In container, 50ml acetone stirring and dissolvings are added in, 5ml water is then added in, is slowly added dropwise and trihydroxybenzophenone equimolar amounts Triethylamine, triethylamine are dissolved in acetone soln and are added dropwise, and are completed after being added dropwise to reaction, reaction solution is stirred down and is poured into In 300ml distilled water, add in chloride solid and dissolve, reaction product is promoted to be precipitated, filter, wash three times, in drying to perseverance, Obtain solid.
In terms of infrared spectrum, diazo naphthoquinone compound is in 3430cm-1 There is the broad peak of moderate strength at place, illustrates in product There are hydroxyl, 2149 cm-1 The absorption at place illustrates that cyano or triple carbon-carbon bonds may be contained in product, but be free of CC in reactant Three keys and the reaction can not generate tri- keys of CC, therefore contain cyano in product, in 1602 cm-1 There is sharp absorption at place Illustrate there is phenyl ring in product, 3433 cm of diazonium naphthoquinone sulphonate-1- OH characteristic absorption peaks weaken, illustrate there has been three hydroxyl of part With diazo naphthoquinone sulfonic acid chloride esterification occurs for base benzophenone.
4 sulfonate modified carbon nanotube of embodiment
Carbon nanotube is immersed in the concentrated sulfuric acid that commercial concentration is 98%, ultrasonic disperse, the reflow treatment 1h at 90 DEG C, It filtering and is washed with deionized water to neutrality, product is dissolved in water, is added drop-wise in aminobenzenesulfonic acid diazonium salt solution by freeze-drying, The mass ratio of carbon nanotube and aminobenzenesulfonic acid diazol is 1:2, it reacts 5 hours, then continues at normal temperatures anti-in a water bath It answers 3 hours, is filtered after reaction, and rinsed with deionized water, freeze-drying obtains product.
The infrared spectrum of sulfonate modified carbon nanotube is shown in that Fig. 3, a are the infrared spectrum of carbon nanotube, and b is sulfonated carbon Nanotube spectrogram.
5 corrosion resistance coating of embodiment
By the alkamine modified epoxy resin of 1kg, 0.5kg silica, 60g pyrrolidones, 0.25kg acrylate, 40gKH-560, water 1.2kg are mixed, and are heated to 30 DEG C, are stirred 2.5 hours, are down to room temperature, obtain coating.
6 light absorption paint of embodiment
Diazo naphthoquinone compound 100g prepared by sulfonate modified carbon nanotube 80g prepared by embodiment 4, embodiment 3, Novolac resin 5.5kg and ethyl lactate solvent 3.5kg are mixed, and are heated to 50 DEG C, are stirred 2 hours, are down to room temperature, Obtain coating.
The preparation of 7 inkstone of embodiment
By calcite 60g, clay 350g, quartz 400, silica modified unsaturated polyester (UP) 180g and curing agent peroxide To change and stirred evenly in methyl ethyl ketone 10g addition blenders, be packed into mold, uniform compaction cures 3 hours at 40 DEG C, obtains parent, Parent is engraved as to the pattern of various needs as needed, black system is carried out to the parent after engraving, makes its smooth, smooth, removes Unnecessary tool marks form anticorrosion layer in corrosion resistance coating prepared by the rub-down ink area coating embodiment 5 of parent, coat and implement in side wall Light absorption paint prepared by example 6 forms light-absorption layer, so as to prepare inkstone.
The corrosion resisting property of 8 inkstone of embodiment
Inkstone prepared by inkstone, marble prepared by inkstone, calcite prepared by embodiment 7 is chosen to be compared.
Black duration is store to ink-stone in 4 DEG C, 20 DEG C or so respectively and carries out simulated experiment, the results are shown in Table 1.
The black duration simulated experiment of 1 ink-stone of table storage
Inkstone of the present invention Calcite inkstone Marble inkstone
4 ℃ 43.0h 5.8h 7.3h
20 ℃ 60.0h 8.6h 11.5h
The results show that the time retained in the inkstone sample aperture that ink is prepared in the embodiment of the present invention 7 is longer, when storage is black A length of 43.0~60.0 h, retention time is appreciably shorter in calcite inkstone and marble inkstone, a length of 5.8 when storage is black~ 11.5h。
Here, it can be seen that dissolution extent is lower, mineral arrangement is close under the microscope, and consistency is high, water penetration effect Difference, storage performance of ink are good.
All above-mentioned this intellectual properties of primarily implementation, there is no this new products of implementation of setting limitation other forms And/or new method.Those skilled in the art will utilize this important information, the above modification, to realize similar execution feelings Condition.But all modifications or transformation belong to the right of reservation based on new product of the present invention.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc. Imitate embodiment.But it is every without departing from technical solution of the present invention content, technical spirit according to the present invention is to above example institute Any simple modification, equivalent variations and the remodeling made still fall within the protection domain of technical solution of the present invention.

Claims (6)

1. a kind of novel ink stone, it is characterised in that：Including inkstone parent and positioned at the anticorrosion layer in rub-down ink area and positioned at inkstone parent The light-absorption layer of side wall；
The raw material for preparing the parent includes calcite, clay, quartz, silica modified unsaturated polyester (UP) and curing agent；
In the parent weight percent of each raw material be respectively calcite 3%~8%, clay 35%~40%, quartz 35%~ 45%th, silica modified unsaturated polyester (UP) 15%~20% and curing agent 1%~2%, the quality sum of each raw material is 100%；
The preparation method of the silica modified polyester includes,
The first step crushes silica, dries at high temperature, sieves with 100 mesh sieve, and often takes the silicon dioxide powder after 300g sievings End, the content for adding in stearic acid sodium in aqueous solution 200ml, the 100ml solution of surface modifier stearic acid sodium are 3g, at room temperature High-speed stirred 30 minutes, filtering, filter cake are washed 3 times with absolute ethyl alcohol, and each ethanol consumption is 30ml, and filtration cakes torrefaction is ground into Powder；
Second step, using 5g rutgers as measurement basis, often added in reaction vessel 5g dimethyl terephthalate (DMT)s, 1,2-PD 10g, tetra-n-butyl titanate 1g are added, nitrogen is passed through in reaction vessel, heat temperature raising is opened after material melts Begin to stir, controlling reaction temperature is in 180 degree；When acid value drops to 8mgKOH/g, temperature is reduced, further adds in 30g maleics Dicarboxylic anhydride, 1,2-PD 330g based on 5g dimethyl terephthalate (DMT)s, continue esterification, control reaction temperature Degree stirs 2 hours~3 hours at 200 DEG C or so, is cooled to 90 DEG C, and insulated and stirred is uniformly to obtain the final product；
Third walks, and powder prepared by the 5g first steps is often taken to be added in the product of second step preparation and is sufficiently stirred, adds in accelerating agent Benzoyl peroxide 0.05g is mixed evenly, and is put into vacuum defoamation in vacuum drying chamber, after normal temperature cure for 24 hours, then is warming up to 90 DEG C of curing 2h, are ground into powder.
2. novel ink stone as described in claim 1, it is characterised in that：It is used to form the raw material of the corrosion resistance coating of the anticorrosion layer Including alkamine modified epoxy resin, silica, water, pyrrolidones, acrylate and KH-560.
3. novel ink stone as claimed in claim 2, it is characterised in that：The weight of each raw material is respectively in the corrosion resistance coating, Relative to the alkamine modified epoxy resin of 100 parts by weight, the dosage of the silica is the parts by weight of 40 parts by weight~50, described The parts by weight of pyrrolidones are the parts by weight of 5 parts by weight~8, and the parts by weight of 20 parts by weight of acrylate~30, KH-560 is 3 parts by weight ~5 parts by weight, in terms of solid, the dosage of the water is the parts by weight of 100 parts by weight~150.
4. novel ink stone as described in claim 1, it is characterised in that：It is used to form the raw material of the light absorption paint of the light-absorption layer Including sulfonate modified carbon nanotube, diazo naphthoquinone compound, novolac resin and ethyl lactate solvent.
5. novel ink stone as claimed in claim 4, it is characterised in that：The parts by weight of each raw material are respectively in the light absorption paint The parts by weight of the parts by weight of sulfonate modified 5 parts by weight of carbon nanotube~10,8 parts by weight of diazo naphthoquinone compound~12, novolaks The parts by weight of the parts by weight of 50 parts by weight of resin~60 and 30 parts by weight of ethyl lactate solvent~40.
6. the preparation method of any inkstone of claim 1 to 5, which is characterized in that including：
Each raw material is added in blender and stirred evenly by the first step, is packed into mold, and uniform compaction cures 3 at 30 DEG C~40 DEG C Hour, obtain parent；
Second step is carved, and parent is engraved as to the pattern of various needs as needed；
Third walks, polishing, and black system is carried out to the parent after engraving, makes its smooth, smooth, removes unnecessary tool marks；
4th step, coating, in the rub-down ink area of parent, coating corrosion resistance coating forms anticorrosion layer, is formed and inhaled in side wall coating light absorption paint Photosphere.
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