CN104193288B - The preparation of a kind of aqueous ceramic anticorrosive paint and painting method - Google Patents
The preparation of a kind of aqueous ceramic anticorrosive paint and painting method Download PDFInfo
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- CN104193288B CN104193288B CN201410408869.XA CN201410408869A CN104193288B CN 104193288 B CN104193288 B CN 104193288B CN 201410408869 A CN201410408869 A CN 201410408869A CN 104193288 B CN104193288 B CN 104193288B
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Abstract
The present invention relates to surface-coating technology, it is desirable to provide the preparation of a kind of aqueous ceramic anticorrosive paint and painting method.The method includes: (1) component A precuring, first adjusts the pH value of water silica sol with catalyst, adds deionized water and composite organic alkane mixes, and stirring reaction obtains component A；(2) B component precuring, grinds after water silica sol, pigment, filler, auxiliary agent each component being mixed, obtains B component；(3) mixing before using, mixes B component with the component A through precuring, by the compounding curing of vibration, stirring or scrolling realization, obtains aqueous ceramic anticorrosive paint.The aqueous ceramic coating VOCs content of the present invention is low, control by alkoxy silane consumption, the VOCs content of last coating can be accomplished less than 100g/L, and the coating environmental protection and energy saving prepared, not only hardness is high, and heat resistance is good, and coating has certain toughness, film is not easily susceptible to cracking, and hardness can improve 1～2H, and shock resistance improves to 20～30cm Kg.
Description
Technical field
The invention belongs to surface-coating technology, be specifically related to a kind of aqueous ceramic coating and painting method thereof.
Technical background
Ceramic coating originates from sol-gel (Sol-Gel) technology of the sixties in 20th century, has established the reason of ceramic coating
Opinion basis.1971, H.Dislich sol-gel process with metal alkoxide for presoma pioneering obtain ceramic oxide
Material, causes a quantum leap of material industry.Aqueous ceramic coating is for metal finishing, a brand-new many merits of protection
Energy, environmental protection, energy-saving coating new product, have abundant raw material resources and wide market development space, and product has preferably
Economic benefit and social benefit.Organic-inorganic nanocomposite coating (inorganic ceramic film) based on aqueous sol-gel technique is led to
Cross the introducing of organic group, make coating not only with toughness and the high intensity of inorganic coating of organic coating, and easy construction, logical
Cross low temperature (150～280 DEG C) solidification i.e. can get high rigidity, corrosion-resistant, wear-resisting, heat-resisting, do not fire, environmental protection, the coating of pottery.
Along with environmental regulation and the appearance of standard, Water-borne modification ceramic coating system (VOCs content is less than 100g/L) is conventional organic solvents
One of heavily contaminated type coating the most potential substitute preparing coating, has broad application prospects.But current is aqueous
Ceramic coating also runs into some problems in actual application, and such as ceramic coating hardness is the highest, hot strength is not good enough, painting
Film easily cracking etc..
Summary of the invention
The technical problem to be solved in the present invention is, overcomes defect of the prior art, it is provided that a kind of aqueous ceramic anticorrosion is coated with
Material.It is a further object to provide the painting method of this aqueous ceramic coating a kind of.
For solving technical problem, the technical solution adopted in the present invention is:
There is provided the preparation method of a kind of aqueous ceramic anticorrosive paint, including the step of two step curings:
(1) component A precuring
Component A is by 20～70% water silica sol, 0.01～2% catalyst, 0～25% deionized water and 25～50%
Composite organic alkane obtains through compounding, and each component is mass percent；Concrete compound process is:
First with catalyst, the pH value of water silica sol is adjusted to the scope of 1.5～4.5, adds deionized water and be combined
Organosilan mixes, and stirring reaction 6～12h obtains component A；
Described catalyst refers to the acidic catalyst for adjusting component A final ph or base catalyst；Wherein,
Acidic catalyst is: one or more in hydrochloric acid, nitric acid, formic acid or acetic acid；Or formic acid and zinc oxide is water-soluble
Liquid；Acetic acid and the aqueous solution of zinc oxide；Or the aqueous solution of formic acid, acetic acid and zinc oxide.
Base catalyst is: ammoniacal liquor or TMAH；
Described composite organic alkane refers to: four alcoxyl class organosilans, three alcoxyl class organosilans, dialkoxy class organosilicon
The mixture of alkane；Its general molecular formula RnSi(OR’)4-n, R is not contain the organo-functional group that oxygen atom is directly connected with silicon atom,
As: alkyl, aryl, γ-glycidyl ether oxygen propyl, γ-methacryloxypropyl；R ' is C1～C5Alkyl, n=0,
1、2；N=0 is four alcoxyl class organosilans, and n=1 is three alcoxyl class organosilans, and n=2 is dialkoxy class organosilan.
(2) B component precuring
By weight percent 35～100% water silica sol, 0～30% pigment, 0～30% filler, 0～5% auxiliary agent will
Grind 2～6h after the mixing of each component, obtain B component；
In B component, described pigment is heatproof inorganic pigment；Described auxiliary agent is defoamer, wetting agent, levelling agent, dispersant
Or one or more in thickener.
(3) mixing before using
B component is mixed by mass ratio A: B=2: 0.5～2 with the component A through precuring, by vibration, stirs or rolls
Dynamic realization compounds curing, obtains aqueous ceramic anticorrosive paint.
As improvement, the pH value of water silica sol of the present invention is 1.5～11, and particle diameter is 10～60nm, aqueous silicon
In colloidal sol, the content of silica is 20～50%, and solvent is water.
As improvement, four alcoxyl class organosilans of the present invention are tetramethoxy-silicane or tetraethoxysilane；Institute
The three alcoxyl class organosilans stated be MTES, MTMS, trimethoxysilane,
KH560 or KH570；Described dialkoxy class organosilan be dimethyldimethoxysil,ne, dimethoxydiphenylsilane, two
Methyldiethoxysilane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxysilane or aminomethyl phenyl diethoxy silicon
Alkane.
As improvement, pigment of the present invention is rutile, titan yellow, iron oxide black, iron oxide red, cobalt black, cobalt blue, cobalt
One or more in green, carbon black, pearl essence and aluminium silver powder, size controlling is within 30 μm.
As improvement, filler of the present invention is silica flour, silicon whisker, aluminum oxide, carborundum, barium sulfate, titanium oxide
In one or more, size controlling is within 30 μm.
Invention further provides the painting method of described aqueous ceramic anticorrosive paint, comprise the following steps:
(1) pre-treatment: metal base carries out pickling, alkali cleaning, blasting treatment, carries out washing and being dried so that it is table afterwards
Face is clean, coarse；
(2) spray painting: after the metal base after process is preheated to 40～80 DEG C, sprays described aqueous ceramic anticorrosive paint
It is coated with on metal base；
(3) sintering curing: the levelling at 140～180 DEG C of the metal base after spraying is dried 5～10 minutes, then is placed in
Sinter 10～30 minutes at 250～280 DEG C, cool down.
The innovative point of the present invention is mainly manifested in 2 points:
Rationally selecting with compounding of () three kinds of different structure alkoxy silanes.The compounding of different structure alkoxy silane has
It is beneficial to later stage polymer sol structure control, and silicon oxide particle sol surface modification controls, thus affect final coating and combine
Close performance；
The utilization of () water silica sol.In the invention, water silica sol is applied at two aspects, first in system
Individually carry out pre-reaction during standby component A with compound alkoxy silane, be so conducive under interference in the participation not having color stuffing
Particle colloidal sols and polymer sol is made to obtain the combination of molecular level by sol-gel technique, and by response parameter
Change can more preferably control the structure of composite water soluble Ludox；Secondly, when preparing composite mortar, silicon is molten plays dispersion and carrier pair
Recast use, so can more preferably control structure and the performance of final coating by the utilization of two aspects of water silica sol.
The invention has the beneficial effects as follows:
The aqueous ceramic coating VOCs content using the present invention is low, by the control of alkoxy silane consumption, last coating
VOCs content can accomplish less than 100g/L, and coating environmental protection and energy saving prepared, not only hardness is high, and heat resistance is good, and
And coating has certain toughness, film is not easily susceptible to cracking, and hardness can improve 1～2H, shock resistance improve to 20～
30cm·Kg。
Detailed description of the invention
First raw material used in the present invention are described in detail:
Water silica sol
Water silica sol in the present invention: pH 1.5～11, particle diameter is 10nm～60nm, receiving of solid content 20%～50%
The silica dioxide granule of meter level dispersion liquid in water.Water silica sol in the present invention as one of inorganic filming substance matter, and
The alkoxy silane generation chemical reaction of hydrolysis, obtains SiO2Network structure so that coating have hardness, corrosion resistance,
The performances such as temperature tolerance.
Water silica sol is all used in the present invention in component A and B component, silane coupled with compound in component A
Agent is reacted, and obtains the mixture containing polymer sol and particle colloidal sols by sol-gel technique, and polymer sol has three kinds
Mode is present in complex sol, and the first is to be physics by chemical bonding to particle water silica sol surface, the second
There is particle water silica sol surface in the mode being wound around, the third is to be distributed in liquid with the form of oligomer；In B component
Water silica sol grinding distribution together with pigment, filler, auxiliary agent, be substantially carried out physics aspect peptizaiton, water silica sol
Existence have the dispersion of beneficially pigment, filler, and the function of diluent can be served as.
Water silica sol in patent of the present invention is divided into acid and alkalescence two kinds, is reacting with composite organic siloxane
Before, with catalyst, pH value is adjusted to 1.5～4.5 scopes.Preferred alkaline aqueous Ludox in the selection of water silica sol.
Catalyst
Owing to commercially available water silica sol is the most acid and two kinds of water silica sols of alkalescence, for obtaining the aqueous of corresponding pH value
Ludox, needs acid and alkaline two kinds of different catalyst that water silica sol pH is transferred to predetermined value.
Acidic catalyst: hydrochloric acid, nitric acid, formic acid or acetic acid one or more；Or the aqueous solution of formic acid and zinc oxide；Acetic acid
The aqueous solution with zinc oxide；Or the aqueous solution of formic acid, acetic acid and zinc oxide.Base catalyst: ammoniacal liquor, TMAH.
Organosilan
Organosilan in the present invention is alkoxy silane, its general molecular formula RnSi(OR’)4-n, R is not for containing oxygen atom
It is directly the organo-functional group being connected with silicon atom, such as: alkyl, aryl, γ-glycidyl ether oxygen propyl, γ-methacryl
Epoxide propyl group；R ' is C1～C5Alkyl, n=0,1,2.It is divided into three according to the alkoxyl number being joined directly together with center Si atom
Class, during n=0, being joined directly together alkoxyl number with Si atom is four, the most referred to as four alcoxyl class organosilans；N=
When 1, being joined directly together alkoxyl number with Si atom is three, the most referred to as three alcoxyl class organosilans；During n=2, with
It is two that Si atom is joined directly together alkoxyl number, the most referred to as dialkoxy class organosilan.
In actual application, the four alcoxyl preferred tetramethoxy-silicane of class organosilan and tetraethoxysilanes；Three alcoxyls
The preferred MTES of class organosilan, MTMS, trimethoxysilane, KH560,
KH570；The preferred dimethyldimethoxysil,ne of dialkoxy class organosilan, dimethoxydiphenylsilane, dimethyl diethoxy
Base silane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxysilane, aminomethyl phenyl diethoxy silane.
Auxiliary agent
Auxiliary agent in the present invention be defoamer, wetting agent, levelling agent, dispersant, thickener one or more.Auxiliary agent
Addition be the 1～10% of coating quality.Auxiliary agent be chosen as general knowledge known in this field, the weight that non-invention is to be studied
Point.Such as, the optional BYK346 of wetting agent, the optional enlightening of defoamer is high by 810.
Pigment
In the present invention, pigment is inorganic pigment conventional on market, and general size controlling is within 30 μm, as coloring
Agent uses, and when the later stage uses, 150～280 DEG C of solidification sintering processes will not lose efficacy, and includes but not limited to: rutile, titan yellow, oxygen
Change iron oxide black, iron oxide red, cobalt black, cobalt blue, cobalt green, carbon black, pearl essence and aluminium silver powder etc..
Filler
In the present invention, Fillers selection includes but not limited to: silica flour, silicon whisker, aluminum oxide etc., carborundum, barium sulfate,
Titanium oxide etc., general size controlling is within 30 μm.
The preparation method of aqueous ceramic anticorrosive paint in the present invention, including the step of two step curings:
(1) component A precuring
Component A is by 20～100% water silica sol, 0.01～2% catalyst, 0～25% deionized water and 5～50%
Composite organic alkane obtains through compounding, and each component is mass percent；Concrete compound process is:
First with catalyst, the pH value of water silica sol is adjusted to the scope of 1.5～4.5, adds deionized water and be combined
Organosilan mixes, and stirring reaction 6～12h obtains component A；
(2) B component precuring
By weight percent 35～100% water silica sol, 0～30% pigment, 0～30% filler, 0～5% auxiliary agent will
Grind 2～6h after the mixing of each component, obtain B component；In B component, described pigment is heatproof inorganic pigment；Described auxiliary agent is froth breaking
One or more in agent, wetting agent, levelling agent, dispersant or thickener；
(3) mixing before using
B component is mixed by mass ratio A: B=2: 0.5～2 with the component A through precuring, by vibration, stirs or rolls
Dynamic realization compounds curing, obtains aqueous ceramic anticorrosive paint.
The specific experiment data of each embodiment are shown in Tables 1 and 2.
In the present invention, the painting method of described aqueous ceramic anticorrosive paint, comprise the following steps:
(1) pre-treatment: metal base carries out pickling, alkali cleaning, blasting treatment, carries out washing and being dried so that it is table afterwards
Face is clean, coarse；
(2) spray painting: after the metal base after process is preheated to 40～80 DEG C, sprays described aqueous ceramic anticorrosive paint
It is coated with on metal base；
(3) sintering curing: the levelling at 140～180 DEG C of the metal base after spraying is dried 5～10 minutes, then is placed in
Sinter 10～30 minutes at 250～280 DEG C, cool down.
Table 1 component A embodiment and composition (unit: Kg)
Table 2 B component embodiment and composition (unit: Kg)
In the present invention, A, B two component mixing after be easy to lost efficacy, need be distributed to finally use with the form packed respectively
Family.Then mix after being weighed voluntarily by end user, by the compounding curing of vibration, stirring or scrolling realization, obtain
Finished product aqueous ceramic anticorrosive paint, for follow-up coating application target.As for B component: the choosing of the mass ratio of component A
Select, by end user according to desired properties (hardness, adhesive force etc.) depending on.
The present invention that listed above is only is embodied as example.It is clear that the invention is not restricted to above example is sub, also may be used
There to be many deformation.All changes that those of ordinary skill in the art can directly derive from present disclosure or associate
Shape, is all considered as protection scope of the present invention.
Claims (3)
1. the preparation method of an aqueous ceramic anticorrosive paint, it is characterised in that include two steps curing step:
(1) component A precuring
Component A is by 20～70% water silica sol, 0.01～2% catalyst, 0～25% deionized water and 5～50% be combined
Organosilan obtains through compounding, and each component is mass percent, and each component summation is absolutely；
Concrete compound process is:
First with catalyst, the pH value of water silica sol is adjusted to the scope of 1.5～4.5, adds deionized water and be combined organic
Silane mixes, and stirring reaction 6～12h obtains component A；
Described catalyst refers to acidic catalyst or the base catalyst of the final ph for adjusting water silica sol；Wherein,
Acidic catalyst is: one or more in hydrochloric acid, nitric acid, formic acid or acetic acid；Or the aqueous solution of formic acid and zinc oxide；Second
Acid and the aqueous solution of zinc oxide；Or the aqueous solution of formic acid, acetic acid and zinc oxide；
Base catalyst is: ammoniacal liquor or TMAH；
Described composite organic alkane refers to: four alcoxyl class organosilans, three alcoxyl class organosilans, dialkoxy class organosilan
Mixture；Its general molecular formula RnSi(OR’)4-n, R is not contain the organo-functional group that oxygen atom is directly connected with silicon atom, is
γ-glycidyl ether oxygen propyl or γ-methacryloxypropyl；R ' is C1～C5Alkyl, n=0,1,2；N=0 is four
Alcoxyl class organosilan, n=1 is three alcoxyl class organosilans, and n=2 is dialkoxy class organosilan；
(2) B component precuring
By weight percent 35～100% water silica sol, 0～30% pigment, 0～30% filler, 0～5% auxiliary agent by each group
Grind 2～6h after dividing mixing, obtain B component；
In B component, described pigment is resistant to elevated temperatures rutile, titan yellow, iron oxide black, iron oxide red, cobalt black, cobalt blue, cobalt green, charcoal
One or more inorganic pigments in black, pearl essence, size controlling is within 30 μm；Described auxiliary agent is defoamer, wetting agent, stream
One or more in flat agent, dispersant or thickener；
(3) mixing before using
B component is mixed by mass ratio A: B=2: 0.5～2 with the component A through precuring, by vibration, stirs or rolls reality
Now compounding curing, obtains aqueous ceramic anticorrosive paint；
The pH value of described water silica sol is 1.5～11, and particle diameter is 10～60nm, the content of silica in water silica sol
Being 20～50%, solvent is water；
Three described alcoxyl class organosilans are KH560 or KH570.
Method the most according to claim 1, it is characterised in that described filler is silica flour, silicon whisker, aluminum oxide, carbon
One or more in SiClx, barium sulfate, titanium oxide, size controlling is within 30 μm.
3. the painting method of aqueous ceramic anticorrosive paint described in claim 1, it is characterised in that comprise the following steps:
(1) pre-treatment: metal base carries out pickling, alkali cleaning, blasting treatment, carries out washing and being dried afterwards so that it is surface is done
Only, coarse；
(2) spray painting: after the metal base after process is preheated to 40～80 DEG C, is sprayed on described aqueous ceramic anticorrosive paint
On metal base；
(3) sintering curing: will spraying after metal base at 140～180 DEG C levelling dry 5～10 minutes, then be placed in 250～
Sinter 10～30 minutes at 280 DEG C, cool down.
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