CN101328387A - Modified self-curing non-chromium zinc based anti-corrosive paint and preparation thereof - Google Patents
Modified self-curing non-chromium zinc based anti-corrosive paint and preparation thereof Download PDFInfo
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- CN101328387A CN101328387A CNA2008100209702A CN200810020970A CN101328387A CN 101328387 A CN101328387 A CN 101328387A CN A2008100209702 A CNA2008100209702 A CN A2008100209702A CN 200810020970 A CN200810020970 A CN 200810020970A CN 101328387 A CN101328387 A CN 101328387A
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Abstract
Modified self-curing anticorrosion paint without a chrome zinc group is prepared from two compositions of modified base material and pigment which are mixed. The modified base material comprises the following compositions in percentage by mass: 37.3 to 53.6 percent of silica sol, 4.1 to 5.7 percent of caustic potash, 9.0 to 13.2 percent of silicon-acrylic latex, 0.3 to 1.0 percent of a pigment dispersant, 0.2 to 1.1 percent of a film forming auxiliary agent, 0.05 to 0.2 percent of a high-efficiency water-based paint antifoaming agent, and deionized water or distilled water serving as the rest. The pigment comprises the following compositions in percentage by mass: 10.1 to 24.2 percent of scaly zinc dust. A preparation method for the modified self-curing anticorrosion paint without the chrome zinc group comprises the following steps of: preparing the modified base material; and preparing the paint. The modified self-curing anticorrosion paint without the chrome zinc group has the advantages of high corrosion resistant property, environmental protection, low energy consumption, etc.
Description
One, technical field
The present invention relates to the green protective system technology in metallic surface, be specially a kind of modified self-curing non-chromium zinc based anti-corrosive paint and preparation method thereof.
Two, background technology
Because zinc-rich paint has good weathering resistance and weldability, now become the most general, the most important priming paint of metal surface protection, be widely used in bridge, boats and ships, storage tank, oil pipeline, outdoor steel construction etc. anticorrosion in atmosphere, the ocean environment.Zinc-rich coating belongs to sacrifice type coating; strong activity by zinc powder can play the galvanic protection effect to the iron-based body; zinc powder corrodes after product can be filled the hole of paint film again, seal the effect that the damage location of filming plays the mask erosion medium, although the therefore very thin corrosion that still can stop iron and steel preferably of zinc-rich coating.
Compare outstanding advantage such as zinc-rich paint has that technology is simple, flexible operation, coating porosity are low with traditional hot spray painted zinc of technical maturity.Spherical zinc powder consumption generally just can play good electro-chemical protection effect in the zinc-rich coating between 85%-90%, and base-material consumption major general is difficult to guarantee the agglutinating value(of coal) of film forming matter.According to film forming base-material difference, zinc-rich paint can be divided into organic zinc-rich paint and inorganic zinc coating.Inorganic filming substance is based on silicate, and has water-solublely, helps environment protection, its shortcoming be dry slow, solidify that influenced by temperature and humidity bigger.
Earlier 1970s, the U.S. has developed sheet zinc-base chromic salts protective coating technique, it is Dacromet Technology, this coating is to be coated on workpiece surface after the mixed solution that zinc flake and aluminium powder, chromic anhydride, wetting agent, dispersion agent, reductive agent, deionized water and other auxiliary agents are formed is stirred, and solidifies down at 300 ℃ then to form.Compare with spherical powder, zinc flake is parallel folded array in filming, and has significantly reduced the infiltration in filming of water and corrosive medium, and the zinc flake consumption of identical coated area, antiseptic property only is 1/3～1/2 of a spherical zinc powder.Because Dacromet Technology is compared with galvanizing with electro-galvanizing, have advantages such as polluting little, high anti-corrosion, no hydrogen embrittlement, oilness, therefore obtained using quite widely at automotive field.The Dacroment coating technology develops rapidly in the world at present, and its application has expanded to medicine, electric power, petrochemical complex and military industry, and more than 30 country has the Dacromet Technology patent right.Yet still there is hexavalent chromium polluted problem in the Dacroment coating.The EOLVD disability regulations that European Union formulated in 1999 have just been carried out strict restriction to chromic content.Stipulate among the 2000/53/EG of Europe, from July 1st, 2003, in each automobile of European production and selling, sexavalent chrome (Cr
6+) content must not surpass 2g.The regulation among the 2000/53/EG has been revised on June 27th, 2002 Europe, and regulation does not allow to contain Cr from July 1st, 2007 the corrosion protection coating that automobile uses
6+, many brand vehicles also take the lead in having formulated the technological standard of no chromiumcoating in the automobile industry of industrially developed country in the world.
Enhancing along with people's environmental protection consciousness; more and more stricter to heavy metal and the restriction that contains volatile organic solvent; non-chromium zinc based coating (being commonly called as chromium-free Dyclo); especially waterborne zinc-rich coating; to become the main flow of green protective system industry development, and be applied to the corrosion prevention of metal construction and component in many industrial circles gradually.Actual exploitation and applicating present situation at aqueous inorganic zinc-enriched coating, answer emphasis to solve following problem at present: (1) with the selection of base-material, be modified as emphasis, to obtain the coating that solidity to corrosion, shock-resistance, snappiness, self cure are better, satisfy broader applications; (2) with selection of pigment, form, be modified as emphasis, thereby obtain the coating that property improves.
Three, summary of the invention
Technical problem: technical problem to be solved by this invention provides a kind of self-curing non-chromium zinc based coating with high anti-corrosion energy, environmental protection, less energy-consumption and preparation method thereof.
Technical scheme: a kind of modified self-curing non-chromium zinc based anti-corrosive paint is formed by modified base material, two kinds of component mixed preparing of pigment: by massfraction, and the component of described modified base material and content: silicon sol: 37.3%-53.6%; Potassium hydroxide: 4.1%-5.7%; Organosilicon crylic acid latex: 9.0%-13.2%; Pigment dispersing agent: 0.3%-1.0%; Film coalescence aid: 0.2%-1.1%; High efficiency water paint antifoaming agent: 0.05%-0.2%; Deionized water or distilled water: all the other.By massfraction, the component of described pigment and content: flake zinc powder: 10.1%-24.2%.
Above-mentioned silicon sol is solid content 24wt%-25wt%, stablizer Na
2The silicon sol of O content 0.3wt%, pH9.0-9.5.
Above-mentioned organosilicon crylic acid latex is the organosilicon crylic acid latex of 36 ℃ of second-order transition temperatures, 31 ℃ of minimum film-forming temperatures, solid content 48 ± 2%, pH7.0-9.0.
Above-mentioned pigment dispersing agent is the waterborne pigment dispersant of solid content 40%, pH8.0.
Above-mentioned defoamer is the water-borne coatings defoamer of solid content 100%, proportion 0.85-0.93.
The sheet of above-mentioned flake zinc powder is thick to be that 0.1 μ m-0.3 μ m, sheet directly are 5 μ m-8 μ m.
A kind of preparation method of modified self-curing non-chromium zinc based coating:
The preparation technology of modified base material: by massfraction, silicon sol 37.3%-53.6%, potassium hydroxide 4.1%-5.7%, distilled water 1%-19.5% are dropped into stirring reaction in the container, after obtaining the high-module potassium silicate solution, it is even to add organosilicon acrylic emulsion 9.0%-13.2%, high efficiency water paint antifoaming agent 0.05%-0.2%, film coalescence aid 0.2%-1.1%, waterborne pigment dispersant 0.3%-1.0% and distilled water 0%-19.55% dispersed with stirring, promptly obtains the organic emulsion modified base material; The preparation of coating: the flake zinc powder of massfraction 10.1%-24.2% is added in the modified base material, fully stir 10min-40min, regulate paint viscosity with distilled water, 80 mesh standard sieves promptly obtain non-chromium zinc based anti-corrosive paint after filtering; The curing of coating: after the test button sandblast that degreasing and rust removal is clean, room temperature dip-coating 1min-5min, paint film is at room temperature placed 20min and is got final product surface drying, can form strong adhesion, salt spray resistance, water-fast, resistant to elevated temperatures non-chromium zinc based anti-corrosion coating behind self cure 20min～24h.
Beneficial effect:
1, using the method for silicon sol and potassium hydroxide reaction to prepare modulus in the zinc based anti-corrosive paint of the present invention in the modified base material component is 5 high-module potassium silicate solution, this method is simple to operate, what obtain is solution-stabilized, the viscosity that stores 0d-5d solution does not have big variation, survey with coating-4 viscosity meter, maintain 10s-19s; And the concentration of solution can be regulated with distilled water, from 5wt%-30wt%.
2, the used modified Portland solution of coating of the present invention, contain the silanol key, when solidifying not only with pigment in zinc can generate chemical bond, near the silanol key of matrix also with matrix on the ferro element reaction generate chemical bond, thereby the coating and the bonding force between the matrix that form not only comprise traditional Van der Waals force, mechanical chelating ability, also comprise chemical bonding force, so it is more firm that coating and matrix bond get, cohesive strength can be brought up to the 0-1 level from the 3-4 level of traditional zinc-rich coating.
3, with organosilicon crylic acid latex the high-module potassium silicate solution is carried out modification among the present invention, make flake zinc powder disperse to become easily, generally stir 5min-30min and can obtain uniform coating; The film-forming properties of the coating after the modification is better, when adopting the dip-coating mode to apply test specimen, and defectives such as specimen surface no sag, holiday, pin hole; In addition, the physicals such as the cohesive strength of coating are improved, and can reach 0 grade; After organic emulsion adds and the inorganic silicic acid salts solution run through combination mutually, form fine and close coating, the solidity to corrosion of coating improves, in the galvanic protection effect test behind the 96h of anti-the neutral salt spray coating intact, acid resistance also doubles.
4, the present invention uses the modification potassium silicate solution to be that binding agent replaces the chromic salt in the Dacroment, and that has realized coating and coating does not have chromaking fully, becomes real ecotypic environmental protection coating material.
5, the binding agent that coating of the present invention adopted; the potassium silicate solution that contains high-module; itself and pigment metallic zinc are mixed with coating under certain atmospheric moisture (not being higher than 85%) and temperature (5 ℃-40 ℃); normal temperature dip-coating 1min-5min; the metallic surface paint film is at room temperature placed 20min and is got final product surface drying, gets final product complete self cure in the 20min-24h, need not at high bake; the coating that forms is firm with matrix bond, can play the good protection effect to matrix, saved the energy to a great extent.
6, coating of the present invention is solvent with distilled water, is different from traditional solvent reducible coatings, and any objectionable impurities of can not volatilizing in air has also been saved the energy greatly; In addition, the viscosity of coating can be regulated by distilled water, thus the mode that thickness that can control coating and selecting applies.
7, the used pigment of coating of the present invention is sheet thick (0.1 μ m-0.3 μ m), sheet footpath (5 μ m-8 μ m) all very little flake zinc powder, (pigment concentration 85%-90%) compares with spherical zinc powder, the content that can reduce pigment is greatly saved cost to 10.1%-24.2%; The coating that forms is that the multilayer zinc powder is formed by stacking, and the shield effectiveness of coating is better, thereby the solidity to corrosion of coating is higher; And the floatability of flake zinc powder is good, is difficult for precipitation in coating, can be uniformly dispersed easilier, and coating property is more stable.
Four, embodiment
Following examples agents useful for same:
| The TH30-B silicon sol | The maritime Science and Technology Ltd. in Nanjing |
| The KR-237 organosilicon crylic acid latex | Nanjing Kang Yi reaches painting company limited |
| The TH-400 waterborne pigment dispersant | The maritime Science and Technology Ltd. in Nanjing |
| TH-504 water-borne coatings high effective antifoaming agent | The maritime Science and Technology Ltd. in Nanjing |
| Flake zinc powder | Taizhou Kechuang polymer company limited |
Embodiment 1
The preparation of modified base material, by massfraction, taking by weighing 37.3% silicon sol (solid content 25%), 4.1% potassium hydroxide, 19.5% distilled water adds in the there-necked flask, stir 10min down 50 ℃-60 ℃ of constant temperature, mixes stirring 40min with 9.0% organosilicon crylic acid latex afterwards, the film coalescence aid of adding 0.2% and 0.05% defoamer and 0.3% dispersion agent, fully stir 60min, leave standstill 2h after, obtain milky finely dispersed modified base material.
During use, take by weighing the flake zinc powder of massfraction 10.0%, slowly add under condition of stirring in the base-material, behind the stirring 50min, the distilled water with 19.55% is regulated the viscosity of coating, filters with 80 purpose standard sieves, promptly obtains zinc based anti-corrosive paint.After the test specimen sandblast that degreasing and rust removal is clean, immerse 1min-5min in the masking liquid, take out nature and drain, form filming of even no sag on the test specimen surface.
Film at room temperature that 20min gets final product surface drying, coating is done solid work behind the 24h, and the coat-thickness of formation is about 35 μ m, coating cross cut test cohesive strength reaches 0 grade, and is firm with bond matrix, and the salt spray resistance ability reaches 500h, high temperature resistant 400 ℃ of 24h coatings are intact, and 40 ℃ of 240h coatings of water resistance test are intact.
Embodiment 2
The preparation of modified base material, press massfraction, get 40.5% silicon sol, 4.3% potassium hydroxide, 14.7% distilled water and add in the there-necked flask, under 50 ℃-60 ℃ of constant temperature, electronic stirring 10min, mix with 9.7% organosilicon crylic acid latex afterwards, electronic stirring 30min, the film coalescence aid of adding 0.5% and 0.09% defoamer and 0.5% dispersion agent fully stir 60min, leave standstill 2h, promptly obtain finely dispersed oyster white organosilicon crylic acid latex modified base material.
During use, take by weighing the flake zinc powder of massfraction 13.3%, slowly add under condition of stirring in the base-material, behind the stirring 30min, the distilled water with 16.41% is regulated the viscosity of coating, filters with 80 purpose standard sieves, promptly obtains zinc based anti-corrosive paint.After the test specimen sandblast that degreasing and rust removal is clean, immerse 1min-5min in the masking liquid, take out nature and drain, form filming of even no sag on the test specimen surface.
This films at room temperature that 20min gets final product surface drying, and coating is done solid work behind the 24h, and the coat-thickness of formation is about 50 μ m, coating cross cut test cohesive strength reaches 0 grade, and is firm with bond matrix, and the salt spray resistance ability reaches 800h, high temperature resistant 400 ℃ of 24h coatings are intact, and water-fast 40 ℃ of 240h coatings are intact.
Embodiment 3
The preparation of modified base material, by massfraction, get 41.5% silicon sol, 5.1% potassium hydroxide, 9.42% distilled water and add in the there-necked flask, under 50 ℃-60 ℃ of constant temperature, electronic stirring 10min, mix with 10.6% organosilicon crylic acid latex afterwards, electronic stirring 30min, the film coalescence aid of adding 0.7% and 0.13% defoamer and 0.65% dispersion agent fully stir 60min, leave standstill 2h, promptly obtain finely dispersed oyster white organosilicon crylic acid latex modified base material.
During use, take by weighing the flake zinc powder of massfraction 17.4%, slowly add under condition of stirring in the base-material, behind the stirring 20min, the distilled water with 14.5% is regulated the viscosity of coating, filters with 80 purpose standard sieves, promptly obtains zinc based anti-corrosive paint.After the test specimen sandblast that degreasing and rust removal is clean, immerse 1min-5min in the masking liquid, take out nature and drain, form filming of even no sag on the test specimen surface.
This films at room temperature that 20min gets final product surface drying, and coating is done solid work behind the 24h, and the coat-thickness of formation is about 80 μ m, coating cross cut test cohesive strength reaches 0 grade, and is firm with bond matrix, and the salt spray resistance ability reaches 1000h, high temperature resistant 400 ℃ of 24h coatings are intact, and water-fast 40 ℃ of 240h coatings are intact.
Embodiment 4
The preparation of modified base material, press massfraction, get 46.5% silicon sol, 5.4% potassium hydroxide, 3.45% distilled water adds in the there-necked flask, under 50 ℃-60 ℃ of constant temperature, electronic stirring 10min, mix with 11.7% organosilicon crylic acid latex afterwards, electronic stirring 30min, the film coalescence aid of adding 0.95% and 0.16% defoamer and 0.84% dispersion agent fully stir 60min, leave standstill 2h, promptly obtain finely dispersed oyster white organosilicon crylic acid latex modified base material.
During use, take by weighing the flake zinc powder of massfraction 21.3%, slowly add under condition of stirring in the base-material, behind the stirring 15min, the distilled water with 9.7% is regulated the viscosity of coating, filters with 80 purpose standard sieves, promptly obtains zinc based anti-corrosive paint.After the test specimen sandblast that degreasing and rust removal is clean, immerse 1min-5min in the masking liquid, take out nature and drain, form filming of even no sag on the test specimen surface.
This films at room temperature that 20min gets final product surface drying, and coating is done solid work behind the 24h, and the coat-thickness of formation is about 100 μ m, coating cross cut test cohesive strength reaches 0 grade, and is firm with bond matrix, and the salt spray resistance ability reaches 1300h, high temperature resistant 400 ℃ of 24h coatings are intact, and water-fast 40 ℃ of 240h coatings are intact.
Embodiment 5
The preparation of modified base material, by massfraction, get 53.6% silicon sol, 5.7% potassium hydroxide, 1% distilled water and add in the there-necked flask, under 50 ℃-60 ℃ of constant temperature, electronic stirring 10min, mix with 13.2% organosilicon crylic acid latex afterwards, electronic stirring 30min, the film coalescence aid of adding 1.1% and 0.2% defoamer and 1.0% dispersion agent fully stir 60min, leave standstill 2h, promptly obtain finely dispersed oyster white organosilicon crylic acid latex modified base material.
During use, take by weighing the flake zinc powder of massfraction 24.2%, under condition of stirring, slowly add in the base-material, behind the stirring 10min, filter, promptly obtain zinc based anti-corrosive paint with 80 purpose standard sieves.After the test specimen sandblast that degreasing and rust removal is clean, immerse 1min-5min in the masking liquid, take out nature and drain, form filming of even no sag on the test specimen surface.
This films at room temperature that 20min gets final product surface drying, and coating is done solid work behind the 24h, and the coat-thickness of formation is about 120 μ m, coating cross cut test cohesive strength reaches 0 grade, and is firm with bond matrix, and the salt spray resistance ability reaches 1600h, high temperature resistant 400 ℃ of 24h coatings are intact, and water-fast 40 ℃ of 240h coatings are intact.
Modified self-curing non-chromium zinc based anti-corrosive paint of the present invention has the kinds of protect function, and the solidity to corrosion height has high scratch resistance and self-healing ability; Excellent water-fast, acidproof, high thermal resistance are arranged; With water is the solvent environmentally safe; Coating normal temperature self cure, energy consumption is low; The binding agent that does not contain chromium does not have injury to environment and human body, can replace some purposes of Dacroment coating.Because this coating safety and environmental protection, the preparation method is easy, energy consumption is few, cost is low, ecology, energy conservation characteristic and anticorrosion, water-fast, resistance to elevated temperatures that it is outstanding, to promote the surface anticorrosion that it is widely used in the large-scale outdoor metal constructions such as bridge, boats and ships, storage tank, oil pipeline in atmosphere, the ocean environment, application prospect is good.
Claims (7)
1. modified self-curing non-chromium zinc based anti-corrosive paint, it is characterized in that: formed by modified base material, two kinds of component mixed preparing of pigment, each component consists of:
A. by massfraction, the component of above-mentioned modified base material and content:
Silicon sol 37.3%-53.6%
Potassium hydroxide 4.1%-5.7%
Organosilicon crylic acid latex 9.0%-13.2%
Pigment dispersing agent 0.3%-1.0%
Film coalescence aid 0.2%-1.1%
High efficiency water paint antifoaming agent 0.05%-0.2%
Deionized water or distilled water all the other
B. by massfraction, the component of above-mentioned pigment and content:
Flake zinc powder 10.1%-24.2%.
2. modified self-curing non-chromium zinc based anti-corrosive paint according to claim 1 is characterized in that:
Described silicon sol is solid content 24wt%-25wt%, stablizer Na
2The silicon sol of O content 0.3wt%, pH9.0-9.5.
3. modified self-curing non-chromium zinc based anti-corrosive paint according to claim 1 is characterized in that:
Described organosilicon crylic acid latex is the organosilicon crylic acid latex of 36 ℃ of second-order transition temperatures, 31 ℃ of minimum film-forming temperatures, solid content 48 ± 2%, pH7.0-9.0.
4. modified self-curing non-chromium zinc based anti-corrosive paint according to claim 1 is characterized in that:
Described pigment dispersing agent is the waterborne pigment dispersant of solid content 40%, pH8.0.
5. modified self-curing non-chromium zinc based anti-corrosive paint according to claim 1 is characterized in that:
Described high efficiency water paint antifoaming agent is the water-borne coatings defoamer of solid content 100%, proportion 0.85-0.93.
6. modified self-curing non-chromium zinc based anti-corrosive paint according to claim 1 is characterized in that:
The sheet of described flake zinc powder is thick to be that 0.1 μ m-0.3 μ m, sheet directly are 5 μ m-8 μ m.
7. the preparation method of a modified self-curing non-chromium zinc based coating is characterized in that:
A. the preparation technology of modified base material: press massfraction, silicon sol 37.3%-53.6%, potassium hydroxide 4.1%-5.7% are dropped into stirring reaction in the container, after obtaining the high-module potassium silicate solution, it is even to add organosilicon acrylic emulsion 9.0%-13.2%, high efficiency water paint antifoaming agent 0.05%-0.2%, film coalescence aid 0.2%-1.1%, waterborne pigment dispersant 0.3%-1.0% and all the other distilled water dispersed with stirring, promptly obtains the organic emulsion modified base material;
B. the preparation of coating: the flake zinc powder of massfraction 10.1%-24.2% is added in the modified base material, fully stir 10min-40min, regulate paint viscosity with distilled water, 80 mesh standard sieves promptly obtain non-chromium zinc based coating after filtering.
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