CN1844279A - Aqueous nano zinc-riched epoxy silicane paint - Google Patents

Abstract

Disclosed is a water-based zinc-rich epoxy silane nano coating material comprising component A and component B, wherein the component A includes (by weight ratio) 800-1000 mesh nano zinc powder 65-80%, epoxy resin 8-25%, ethanol 0.1-5%, deionized pure water 0.5-5 wt%, thickening agent 0.1-1%, and anti-settling agent 0.1-3%, and the components B includes combination of bis-silyl aminosilane and vinylsilane 1.5-5%, and hardening agent 3-8%.

Description

Aqueous nano zinc-riched epoxy silicane paint

Technical field

This patent is being the non-solvent water-repellent preservation priming paint that is mainly used in the metallic surface (or being called end property coating) of main raw material from newborn type Resins, epoxy and silane and nano zinc powder.

Background technology

Traditional coating mostly is solvent-borne type greatly, and the content height of volatile organic compounds (VOC) causes environmental pollution.Water-borne coatings since VOC content seldom, construction process does not have fire hazard, is environmental friendliness coating, obtains global greatly developing, and has now surpassed 50% of total consumption.

In waterborne metal anti-corrosive paint (priming paint) field that this patent relates to, there are three big R﹠D directions to be worth paying close attention to: 1. traditional aqueous inorganic zinc-enriched coating, the history in more than 50 year of its development experience, its ground and marine atmosphere, hot environment that surface corrosion is not removed fully all shows excellent performance.When the place of coating local failure is subjected to water or ionogen erosion, zinc-rich coating and metal body constitute corrosion cell, suppress the corrosion on metal body (negative electrode) surface to sacrifice zinc powder (anode) on one's own initiative, thereby play electro-chemical protection effect the metal body; But there is gap aspect the excellent characteristic of modern organic coatings such as film-forming properties, molecule interpenetrating(polymer)networks connectivity.2. aqueous epoxide resin paint, it is the hot topic of current research and development, the prescription kind is also more, and Resins, epoxy itself has good physical chemistry film forming properties, and the selection of other compositions of the key of research and development in prescription promotes effect to Resins, epoxy in conjunction with the physical chemistry over-all properties that produces; Current performance preferably the anticorrosion epoxypaint of water-based metal mainly in the electrophoretic paint field.3. Waterborne Silicon-Contained Polymer Coatings, with siloxane bond (is that the polysiloxane (silicone resin) that skeleton is formed belongs to macromolecular compound partly organic, half inorganic structure Si-O-Si-), they have organic and inorganic characteristic concurrently, the chemical physical stability of inorganic nature can be that other macromolecular materials are not available, is the paint field of current tool development prospect.The nineteen fifty-nine U.S. " DOW CORNING " company has begun to apply for since the poly-silicon coating patent that various countries drop into a large amount of research and development ability exploitation silane coatings in this field, the organosilane monomer of research and development and polymkeric substance diversity, and various coating are very impressive; Have remarkable thermotolerance, erosion resistance and can be widely used in fields such as aviation, ships, machinery, building, weaving, leather.But water-fast vapour permeability is relatively poor, and the water solvent ratio is excessive, and surface drying is slow, the cementability relative mistake.

Rose in 1992 by U.S. Department of Defense's Air Research Laboratory and subsidize the silane process of surface treatment research of carrying out metal in material system of U.S. University of Cincinnati energetically, more strong, the research tendency in this school of inventor's long-term follow is so that avoiding detours aspect the silane additives of coating.It can be relevant representative by disclosed CN 1360644A of 2002.7.24 day in Chinese patents; " aqueous mixture with vinyl silanes and bis-silyl aminosilane is handled the protectiveness of metallic surface " proposed; this patent proposed multiple combination silane component and deal (account for mixture total concn about 6%) thereof; it is the place that this patent will be used for reference; other compositions are about 94%---water, optional solvents, optional PH conditioning agent, the ratio of water and solvent can be water entirely or is solvent entirely from 0～～95%.The inventor herein carries out verification experimental verification with this prescription; when " water " composition 50%; natural room temperature can be not dry with interior moisture in 20 60 seconds above times of degree---is not inconsistent with the effect of this patent statement; there was not drying in 60 minutes yet; retaining of moisture content can be accelerated corrosion of metal rather than protection anti-corrosion of metal; this patent makes this professional those of ordinary skill can not implement or realize after having seen this technical scheme, does not meet publicity, the practical principle of patent application and mandate.This patent claims the preservative effect of zinc-plating material is better than non-zinc-plating material, can infer not contain zinc in the solution or content is few.In addition, this patent is if its solvent composition of rapid drying will be higher than 50% at least, and this is the superseded coating class of non-environmental protection---and can not be called " water-based ", should be " solvent-borne type ".

Its patent at U. S. application has tens, is relevant representative with disclosed No. 2005179011 patent Superprimer of 2005.8.18 day, and main points are at What is claimed is:

1.A hydrophilic composition capable of coating a substrate and curing to provide a hydrophobicfilm inhibiting corrosion，the composition comprising：a bis-silane comprising between about 5percent to about 40 percent of the composition；a water soluble or dispersible polymer；a watersoluble solvent；and nanoparticles having a mean particle size of ranging between about 0.01nanometers to about 500 nanometers.

5.The composition of claim 1，wherein：the bis-silane comprises between about 10 percent toabout 25 percent of the composition；the nanoparticles comprise between about 5 percent to about25 percent of the composition；the water soluble or dispersible polymer comprises between about10 percent to about 30 percent of the composition；and the water soluble solvent comprisesbetween about 10 to about 87 percent of the composition.

8.The composition of claim 1，wherein the water soluble or dispersible polymer and thenanoparticles comprise more than 50 percent of the composition.

9.The composition of claim 1，wherein the water soluble or dispersible polymer includes an epoxyresin.

In " super priming paint " prescription: two silane account for 5～～40%, nano powder 5～～25%, polymkeric substance 10～～30%, water solvent 10～～87%.

CN 1360644A and No. 2005179011 patents with enumerate a large amount of silane compositions and mutually combination determine too wide right face---compare the example that its concrete enforcement can be verified, substantially exceeded the supported degree of embodiment, have one to be false or one of not creative or three property in the hundreds of prescription, this patent will be false or part is false.

Rust-preventing characteristic and Corrosion Protection excellence through the metallic surface that silane treatment is crossed, the statement that these are a large amount of in numerous data.Since the later stage nineties in last century, certain research was done to the Corrosion Protection that silane is used for ferrous metal and non-ferrous metal surface by domestic University Of Chongqing, Tongji University, Zhejiang University, East China University of Science, the Chinese Academy of Sciences and some enterprises.

With three big advantages: waterborne zinc-rich coating, aqueous epoxide resin paint, the Waterborne Silicon-Contained Polymer Coatings complementary simultaneously limitation separately that combines is current forward position research direction, also is the direction and the purpose of this patent research.

Consult the relevant data of water-borne coatings, think that " water-borne coatings " book of " organosilicon macromolecule and the application thereof " book of 2004.6 months first versions of Chemical Industry Press and 2006.2 months first versions can summarize the substance in current domestic and international water-borne coatings and silane field.2006.4.1 day retrieval Chinese patent database is with title: coating or lacquer AND summary: epoxy and silane and zinc, retrieval obtains two parts of patent: CN91103183.9, CN01140874.X; With: summary: epoxy and silane and zinc, retrieval obtains seven parts of patents.Wherein: CN01140874.X and this patent are more approaching, and its content Description is as follows: on December 7th, 2005 was announced, patent No. CN 01140874.X title: water two-component protective paint composition; Form, fill a prescription:

A) first kind of component: (i) 3-aminopropyltriethoxywerene werene; (ii) formic acid, its consumption is enough to reach pH value 7-9; (iii) a kind of compound is selected from 3-glyceryl oxygen propyl trimethoxy silicane and 3-glyceryl oxygen propyl-triethoxysilicane, and the amido hydrogen equivalent in several-aminoalkyl group trialkoxysilanes that its consumption makes is 4--6 with the ratio of the epoxide equivalent of described compound; (iv) one or more pigment, wherein at least 50 weight % have electroconductibility; B) second kind of component: (v) finely disintegrated zinc, zinc is 1 with the gross weight ratio of pigment: 1-4: 1; Solid binder is 1 with the ratio of zinc and total pigment weight: 20-1: 60.

Mainly form by following steps:

(i) water is mixed with at least a aminosilane, form first kind of mixture; (ii) be up under 40 ℃ the temperature, add at least a strong acid in first kind of mixture, usage quantity is enough to reach pH value 7-9, forms second kind of mixture; (111) with one or more colo(u)rant dispersion in second kind of solution, wherein said pigment at least 25 weight % have electroconductibility, form the third mixture; (iv) be up under 40 ℃ the temperature, add at least a epoxy silane in the third mixture, the amido hydrogen equivalent in the aminosilane and the epoxy equivalent (weight) of epoxy silane be than being 3-7, thereby obtain first kind of component.

2006.4.1 day retrieval United States Patent (USP) database, patent retrieval from calendar year 2001 with: ACLM/ZINC ANDACLM/EPOXY AND ACLM/SILANE retrieval obtains 107 parts of patents; 2006.4.28 day obtain 85 parts of patents with: ACLM/EPO$AND ACLM/VINYL$ AND ACLM/BIS$ AND ACLM/ (ZINE OR ZN) retrieval, add AND ACLM/ (COATING OR PAINT) just only retrieval obtain 27 parts of patents.Think dependency after all reading all not as good as No. 2005179011 above-mentioned patents, therefore be the no longer statement of saving space.

From above retrieval situation, with three big advantages: waterborne zinc-rich coating, aqueous epoxide resin paint, the Waterborne Silicon-Contained Polymer Coatings complementary simultaneously circumscribed achievement in research quantity and seldom but begun to take shape and all concentrate control in world-class large-size chemical industrial separately that combines, domestic enterprise and research and development institution also do not have the place.The main points of coating research are in the raw material of recipe ingredient, the selection of ratio, difficulty will digest a large amount of domestic and international forward position data, will screen from a large amount of raw materials and ratio, make up, verify repeatedly its performance, perhaps a little difference of component, ratio just determines the quality of coating.

Summary of the invention

The aqueous nano zinc-riched epoxy silicane paint prescription is achieved in that

Weight with whole components is 100%, below is the weight ratio of each component:

A component: 800～1000 order nano zinc powders 65%～80%

From newborn type Resins, epoxy 8%～25%

Ethanol 0.1%～5% deionization pure water 0.5%～5%

The heavy agent 0.1%～3% of viscosifying agent 0.1%～1% anti-branch,

B component: silane combination: [bis-silyl aminosilane, vinyl silanes] 1.5%～5%

The combination matching rate of these two kinds of silane between 0.15～0.30,

Solidifying agent 3%～8%.

B component 1: the silane combination: [bis-silyl aminosilane, vinyl silanes] has following combination right:

Vinyl acetoxysilane and two-(trimethoxy-silylpropyl) amine;

B component 2: the silane combination: [bis-silyl aminosilane, vinyl silanes] has following combination right:

Vinyltriacetoxy silane and two-(triethoxysilylpropyltetrasulfide) amine;

Vinyltriacetoxy silane and two-(trimethoxy-silylpropyl) amine;

Vinyltriethoxysilane and two-(trimethoxy-silylpropyl) amine;

Vinyltriethoxysilane and two-(triethoxysilylpropyltetrasulfide) amine;

Vinyltrimethoxy silane and two-(trimethoxy-silylpropyl) amine;

Vinyltrimethoxy silane and two-(triethoxysilylpropyltetrasulfide) amine.

Aqueous nano zinc-riched epoxy silicane paint be on the basis of reference CN 1360644A patent to inventor herein's patent formerly: application number: 200610054213.8, further development and innovation, the silane combination of wherein having digested and assimilated CN 1360644A patent: [bis-silyl aminosilane, vinyl silanes]---be that this patent B component 2 has carried out innovation again with other composition and formula rate and obtains good effect.

Aqueous nano zinc-riched epoxy silicane paint primer film surface drying 5 minutes, after 20 minutes paint film can be anti-the nickel coin scraping, with the cementability of metal be 5B, for non-zinc-plating material excellent performance is arranged; Overcome a large amount of waters of CN 1360644A patent or used solvent---the shortcoming of the slow and non-environmental protection of surface drying.

Aqueous nano zinc-riched epoxy silicane paint is patent formerly: application number: 200610054213.8, component and ratio further optimize and expansion, make the right formula range of original single silane combination that bigger selectivity and adaptability to different initial conditions be arranged, thus to the different metal base material further select pointedly prescription with improve antiseptic property, cost can reduce pointedly.

Embodiment

Prepare the A component: after various material requesteds in this component are chosen by weight percent recited above, earlier in stirrer, stirring together 10～20 minutes from newborn type Resins, epoxy, ethanol, deionization pure water, again zinc powder is put into lentamente in the liquid that is stirred, needed to stir 20 minutes.Add viscosifying agent then, prevent dividing heavy agent stirring airtight after 10～20 minutes.

Preparation B component: silane is made up stirring in stirrer 20 minutes with modification fat amine curing agent.

Preparation A, B component: after the A for preparing, B component mixed and stir 30 minutes, pH value was controlled in 6～8, makes.

The contrast protection against corrosion detects: epoxy zinc-rich paint, a kind of of aqueous nano zinc-riched epoxy silicane paint are brushed respectively on the steel plate sample of equal amts, treat that the detected result after its curing is as shown in the table:

Test item	Neutral salt spray test (NSS), film thickness measurement, sticking power (cross-hatching)
		The sample title:	Epoxy zinc-rich paint steel plate sample, aqueous nano zinc-riched epoxy silicane paint steel plate sample
Detect foundation: evaluating basis:	GB/T1771-1991、GB/T9286-1998、GB/T4956-1985 ASTMD1654-1992、GB/T9286-1998

Sample was through 480 hours neutral salt spray test detected results

The sample title	Thickness average value (μ m)	The monolateral corrosion width of drawn area (mm)	The corrosion grading
				Epoxy zinc-rich paint steel plate sample	(71.0 paint film thickness is 3.88 times of water base silane primer)	1.0	7
Aqueous nano zinc-riched epoxy silicane paint steel plate sample	18.3	(0.2 being better than 5 times of epoxy zinc-rich paint)	9 (being better than 2 grades of epoxy zinc-rich paint)

Sticking power (cross-hatching) detected result

The sample title	Sticking power (cross-hatching) grade
		Epoxy zinc-rich paint steel plate sample	2
Aqueous nano zinc-riched epoxy silicane paint steel plate sample	1 (being better than 1 grade of epoxy zinc-rich paint)

By detected result as can be known, as anti-corrosion primer, aqueous nano zinc-riched epoxy silicane paint is higher than 1 grade of epoxy zinc-rich paint commonly used to the tack of metallic matrix, and erosion-resisting ability is better than 5 times of epoxy zinc-rich paint.Anti-scratch characteristic, quick-drying behind the aqueous nano zinc-riched epoxy silicane paint film surface drying and be lower than the VOC value that environmental protection standard limits, be epoxy zinc-rich paint and existing other heavy anti-corrosion primer paint film incomparable.

But every liter of this water-based paint is 5 times of every liter of coated area of epoxy zinc rich primer with 25 square metres of 0.35 millimeter thickness overcoatings, every square metre few 0.2 yuan of price.Have excellent non-corrosibility and to each metalloid and paint cementability, but attenuate zinc-rich paint layer thickness.

This environment-friendly water-based nano zinc-riched epoxy silicane paint rete protection against corrosion phase reaches 6-8, but and overcoating.

Purposes: can be used for the sea transport freight container, bridge, steelframe, pipeline, railing and all kinds of hardware.

The basic parameter of aqueous nano zinc-riched epoxy silicane paint

Packing	2 components
						Color	Grey is unglazed
Flash-point	N/A (water-based)
						Density	1.67g/cm 2
Viscosity	60-170 Centistokes，(10-15sec，#4 Zahn Cup)
						Solids content	～84％
Theoretical consumption	Can be coated with 25 square metres/every liter, thick 35 μ m calculate with rete
						Time of drying (25 ℃)	Surface drying: 3～5 minutes, can anti-nickel coin scraping after 20 minutes
Completely solidified: 6-8 hour
					Thermostability		＞150℃
Supporting paint class	Resins, epoxy, chlorinated rubber, Polyurethane, ethene and solubility finish paint etc.
						VOC	Organic volatile 96 grams/every liter
Surface preparation	The processing of sandblasting, cleaning is also dry, surperficial oil stains-less
						Coating process	Airless spraying, aerial spraying, roller coating is brushed
Construct duration of service	Packing is opened the operational time of back: more than 8 hours
						The priming paint shelf life	12 months
Build	20-50μm
						Surface drying time (in minute)	Temperature	5℃	20℃	50℃	80℃
Shortest time	N/A	3min	2min	1min
					Maximum duration		N/A	7min	5min	3min

Claims (3)

1. an aqueous nano zinc-riched epoxy silicane paint has two kinds of components, and its prescription feature is:

Weight with whole components is 100%, below is the weight ratio of each component:

The A component: 800～～1000 order nano zinc powders 65%～80%,

From newborn type Resins, epoxy 8%～25%,

Ethanol 0.1%～5%, deionization pure water 0.5%～5%,

Viscosifying agent 0.1%～1%, the heavy agent 0.1%～3% of anti-branch;

B component: silane combination: [bis-silyl aminosilane, vinyl silanes] 1.5%～5%,

The combination matching rate of these two kinds of silane between 0.15～0.30,

Solidifying agent 3%～8%.

2. a kind of aqueous nano zinc-riched epoxy silicane paint according to claim 1, its prescription feature is:

The B component: the silane combination: [bis-silyl aminosilane, vinyl silanes] has following combination right:

Vinyl acetoxysilane and two-(trimethoxy-silylpropyl) amine.

3. a kind of aqueous nano zinc-riched epoxy silicane paint according to claim 1, its prescription feature is:

B component: silane combination: [bis-silyl aminosilane, vinyl silanes 1 have following combination right:

Vinyltriacetoxy silane and two-(triethoxysilylpropyltetrasulfide) amine;

Vinyltriacetoxy silane and two-(trimethoxy-silylpropyl) amine;

Vinyltriethoxysilane and two-(trimethoxy-silylpropyl) amine;

Vinyltriethoxysilane and two-(triethoxysilylpropyltetrasulfide) amine;

Vinyltrimethoxy silane and two-(trimethoxy-silylpropyl) amine;

Vinyltrimethoxy silane and two-(triethoxysilylpropyltetrasulfide) amine.