CN108291006A

CN108291006A - Epoxy primer coating

Info

Publication number: CN108291006A
Application number: CN201680066439.1A
Authority: CN
Inventors: 沈岳; 洪亮; 陈洪英
Original assignee: Blue Cube Intellectual Property Co Ltd
Current assignee: Blue Cube Intellectual Property Co Ltd; Blue Cube IP LLC
Priority date: 2015-11-16
Filing date: 2016-11-15
Publication date: 2018-07-17
Also published as: TW201728708A; WO2017087392A1

Abstract

There is provided herein a kind of coating composition, the coating composition includes (a) composition epoxy resin, and the composition epoxy resin includes the reaction product of the following terms：(i) reactant of epoxy resin, the compound of (ii) containing cashew nut phenol moieties and (iii) selected from or mixtures thereof carboxylic acid, phenolic compound；(b) amino crosslinker compound.The present invention also provides a kind of method being used to prepare curing coating composition and include the article of the coating composition.

Description

Epoxy primer coating

Technical field

The disclosure relates generally to epoxy primer coating compositions and its purposes.

Background of invention

Epoxy resin is one of most important classification of thermosetting polymer, is largely used to protect in many coating industries Property coating.However, epoxy resin is frangible in solidification；And flexible (such as the T shapes bending of the difference of epoxy resin>2T) limit this Application of the based epoxy resin in coil primer coating.Thus it is common to use known flexible polyester resin replaces epoxy resin； And with being blockaded polyisocyanates come curing polyester resin to form cured primer coating.However, and epoxy resin system It compares, shows poor anti-corrosive properties (for example, the scribing line distance after test is more than 8.5mm) property using the primer coating of polyester resin Energy.

In addition, at present primer coating solid content typically too low (for example, 50wt% or less) and be not used to Primer coating application.Therefore, the solid content of curable primer coating composite is elevated above to the level (example of 50 weight % Such as 60 weight % or higher levels) it will be advantageous.High solid coating helps to reduce required solvent in coating composite Amount so that the composite shows enough viscosity to allow the composite to flow and process the composite.Such combination Object must be careful to and prepare in a controlled manner, to provide the resin for the viscosity that can be used for coating application.In turn, allotment is reduced The solvent loading of object can be provided with the coating composite compared with low VOC (VOC).VOC rows in coating industries It puts and is limited by environmental legislation；And the coating composite with reduced VOC emission is provided and is made of this class composite Coating come the influence for reducing to environment be beneficial.

Therefore, the industrial primer coating composition that can be cured that provides is advantageous, the curable primer coating group Close object can assign the cured primer coating made of this class curable compositions with improve property (such as high mechanical properties, High-temperature behavior, high flexibility and high antiseptic property) balance combination.Meanwhile primer coating composition can be discharged into environment it is less Volatile organic compounds (VOC) emission.The present invention solves the above problem.

Brief summary of the invention

In various aspects of the disclosure, a kind of primer coating composition based on composition epoxy resin, profit are provided With the article of these primer coating compositions and preparation and the method for curing these compositions.

One aspect of the present invention covers coating composition, and the coating composition includes (a) a concentration of about 25 weight % To the composition epoxy resin of about 35 weight %, and (b) amino crosslinker compound.

Another aspect of the present disclosure covers the technique for preparing solidify coating.The technique includes providing curable coating combination Object, the curable coating composition include the composition epoxy resin and (b) amino of (a) about 25 weight % to about 35 weight % Crosslinker compound；With curable coating composition is heated to about 100 DEG C to about 300 DEG C of temperature to form solidify coating.

Another aspect of the present disclosure provides a kind of article, and the article includes substrate and adheres to substrate surface at least The coating of a part, wherein the coating is prepared by applying the coating composition comprising the following terms：(a) about 25 weight Measure the composition epoxy resin of % to about 35 weight %, and (b) amino crosslinker compound.

Other characteristics and the repetition of the present invention are more fully hereinafter described.

Schema is sketched

Patent or application documents at least contain a colored drawing.The colored drawing pair of this patent or Patent Application Publication This will be by office according to requiring to provide and pay necessary expense.

For the purpose of the present invention is illustrated, attached drawing shows the form of the currently preferred present invention.It will be appreciated, however, that this Invention is not limited to embodiment shown in attached drawing.

Fig. 1 is the schematic cross sectional views for the part for showing the primer coating film on metallic plate.

Fig. 2 is show backing coating in the part and primer coating film of the primer coating film on metallic plate schematic Sectional view.

Fig. 3 is the schematic cross sectional views for showing the substrate with various layers, and the layer is included in the top surface of metal substrate On primer coating film layer and backing coating and the primer coating film layer on the bottom surface (or back side) of same metal substrate With backing coating.

Fig. 4 is to show the schematic cross sectional views with several layers of substrate, and the layer is included in the top surface of metal substrate Primer coating film layer, backing coating, pretreatment layer and zinc layers in (or front surface) and the bottom surface in same metal substrate Primer coating film layer, backing coating, pretreatment layer on (or back side) and zinc layers.

Fig. 5 is a series of three photos of F-7 primer coatings composite (referring to embodiment 7) on a metal plate, is shown Show the result of film surface property of the salt spray test before and after 7 days.Figure (A) has the original of scribing line before being shown in salt spray test Beginning coated film；Scheme (B) and shows the coated film after salt spray test；And scheme (C) display to scrape to measure the compacted of corrosion along scribing line The coated film of variate (distance).

Fig. 6 is a series of three photos of comparison F-E primer coating composites on a metal plate, is shown in salt fog survey The result of film surface property before and after trying 7 days.Figure (A) has the original coating of scribing line before being shown in salt spray test Film；Scheme (B) and shows the coated film after salt spray test；And scheme (C) display along scribing line scrape with measure corrosion creep value (away from From) coated film.

Fig. 7 is a series of three photos of comparison F-G primer coating composites on a metal plate, is shown in salt fog survey The result of film surface property before and after trying 7 days.Figure (A) has the original coating of scribing line before being shown in salt spray test Film；Scheme (B) and shows the coated film after salt spray test；And scheme (C) display along scribing line scrape with measure corrosion creep value (away from From) coated film.

Fig. 8 is a series of three photos of F-8 primer coatings composite (referring to embodiment 8) on a metal plate, is shown The result of the film surface property before and after salt spray is tested 7 days is shown.Figure (A) has scribing line before being shown in salt spray test Original coated film；Scheme (B) and shows the coated film after salt spray test；And scheme (C) display to be scraped along scribing line to measure corrosion Creep value (distance) coated film.

The detailed description of the present invention

The disclosure provides the epoxy primer coating composition for including composition epoxy resin and amino crosslinker compound.This A little primer coating compositions are once applied to metal substrate and cure, and are provided with many beneficial attributes, such as high machinery is by force Degree, high-temperature behavior, high flexibility, high antiseptic property, and with low VOC (VOC) discharge.

(I) primer coating composition

An aspect of this disclosure provides the primer coating comprising composition epoxy resin and amino crosslinker compound Composition.In general, primer coating composition is curable primer coating composition.

(a) composition epoxy resin

In general, composition epoxy resin includes the reaction product of the following terms：Epoxy resin, the change containing cashew nut phenol moieties Close object and the reactant selected from or mixtures thereof carboxylic acid, phenolic compound.

In general, the compound containing cashew nut phenol moieties and the reaction containing reactive group (such as hydroxyl or carboxylic acid group) Agent is all reacted with the epoxy group in epoxy resin.When epoxy resin is to the ratio of the compound containing cashew nut phenol moieties and reactant When rate is close to stoichiometry, reaction product usually has high molecular weight.If epoxy resin is significantly excessive, final reaction production Object usually contains a large amount of remaining epoxy resin and epoxy group.On the contrary, if the compound containing cashew nut phenol moieties and reaction Agent is excessive, then most of epoxy groups are usually consumed by reactive hydroxyl and carboxylic acid group.In addition, if in epoxy resin group It closes in object without using the range being detailed below, then may lead to unacceptable viscosity or unacceptable epoxide equivalent (EEW) With different T_dProperty.

In general, the weight percent of primer coating composition epoxy resin composition can be in 25 weight % to about 35 weights In the range of amount %.In each embodiment, the weight percent of composition epoxy resin can be in about 25 weight % to about 35 Weight %, about 26 weight % are to about 34 weight %, about 28 weight % to about 32 weight % or 29 weight % to about 31 weight %'s In range.In one embodiment, the weight percent of primer coating composition epoxy resin can be about 26 weight %. In another embodiment, the weight percent of primer coating composition epoxy resin can be about 28 weight %.Another In embodiment, the weight percent of primer coating composition epoxy resin can be about 30 weight %.

(i) component of composition epoxy resin

Epoxy resin.Many epoxy resin can be used for preparing composition epoxy resin.In general, epoxy resin is curable 's.The epoxy resin both mechanically and thermally of any modified epoxy resin composition can be used in this ability.Epoxy resin or The non-limiting embodiment of polyepoxide includes aliphatic, cycloaliphatic, aromatic series, heterocyclic epoxy compounds and its mixing Object.In a preferred embodiment, epoxy resin can be averagely containing at least one reactive ethylene oxide group.It can be used for this Epoxy resin in composition epoxy resin used in text includes (for example) monofunctional epoxy resin, multifunctional or poly- functional epoxy tree Fat and a combination thereof.In some embodiments, the preparation of the epoxy resin and this based epoxy resin that can be used in the present invention discloses In (for example) Lee, H. and Neville, K., Handbook of Epoxy Resins, McGraw-Hill Book Company, New York, the 1967, the 2nd chapter, in the 2-1 pages to the 2-27 pages, the document is incorporated herein by reference.Epoxy resin it is detailed Thin description and preparation also can be found in International Patent Publication No. WO 2008/045894, and the patent is herein incorporated by reference In.

In preferred embodiments, epoxy resin can be in liquid form, referred to as liquid epoxies (LER).It can be used for The non-limiting embodiment of liquid epoxies in the present invention may include (but not limited to) D.E.R.^TM331； D.E.R.354^TM；D.E.R.332^TM；D.E.R.330^TM；D.E.R.383^TM；With its mixture.Above-mentioned D.E.R. epoxy resin is The commodity that can be obtained from Dow Chemical.

Compound containing cashew nut phenol moieties.The compound of a variety of phenol moieties containing cashew nut can be used for preparing epoxy composite Object.Suitable part of compounds containing anacardol includes (for example) anacardol, compound (such as the cashew nut containing cashew nut diphenol part Diphenol) and its mixture.The exemplary embodiments for the compound containing cashew nut phenol moieties that can be used in the present invention include epoxy The anacardol of change, the anacardol of epoxy resin modification, cashew nut shell oil (cashew nutshell liquid, CNSL), anacardol Base acid anhydrides and its mixture.The detailed description of compound containing cashew nut phenol moieties and preparation can be found in International Patent Publication No. WO 2014/117351, the patent is incorporated herein by reference.

In another embodiment, the compound containing cashew nut phenol moieties can be that (for example) the shrink made of CNSL is sweet Oily ether.The glycidol ether made of CNSL compounds can be in " Epoxy resin from cardanol as partial replacement of bisphenol-A-based epoxy for coating application”, J.Coat.Technol.Res., 2014, one or more compounds described in 11,601-618, the document is with the side of reference Formula is incorporated herein.

One of beneficial property of the part of compounds containing anacardol is their hydrophobicity, provides the composite for repelling water, Because water can promote the corrosion of metal material.

Epoxy resin to the molar ratio of the compound containing cashew nut phenol moieties can with and will change.In general, epoxy resin It can be 1 to the molar ratio of the compound containing cashew nut phenol moieties:0.05 to about 1:In the range of 0.75.In each embodiment In, epoxy resin can be about 1 to the molar ratio of the compound containing cashew nut phenol moieties:0.05 to 1:0.75, about 1:0.10 arrives About 1:0.5, about 1:0.20 to about 1:0.40 or about 1:0.25 to about 1:0.30.

Reactant.In general, reactant is or mixtures thereof carboxylic acid, phenolic compound.In each embodiment, reactant Can be carboxylic acid or dicarboxylic acids.Each in these carboxylic acids can contain 2 to about 34 carbon in aliphatic or aromatic moiety Atom.The non-limiting embodiment of carboxylic acid can be acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, Undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, amber Amber acid, glutaric acid, adipic acid, glycolic, gluconic acid, lactic acid, malic acid, tartaric acid, ascorbic acid, glucuronic acid, Malaysia Acid, fumaric acid, pyruvic acid, aspartic acid, glutamic acid, benzoic acid, ortho-aminobenzoic acid, methanesulfonic acid, 4-HBA, benzene second Acid, mandelic acid flutter acid (pa is not sour), oxalic acid, malonic acid, succinic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, tridecane Diacid, dodecanedioic acid and hexadecandioic acid (hexadecane diacid).In other embodiments, reactant can be phenol.It can be used for preparing asphalt mixtures modified by epoxy resin The phenolic compound of oil/fat composition includes that (for example) there are two the aromatic groups (i.e. bis-phenol) of hydroxy functional group for tool.These phenols The non-limiting embodiment of compound can be bisphenol-A, bisphenol-ap, bisphenol AF, bisphenol b, bisphenol b P, bisphenol-c, bis-phenol E, bis-phenol F, bis-phenol G, bis-phenol M, bis-phenol P, bis-phenol PH, bisphenol S, bis-phenol TMC and bisphenol Z.

Epoxy resin to the molar ratio of reactant can with and will change.In general, molar ratio of the epoxy resin to reactant It can be about 1:0.50 to about 1:In the range of 1.4.In each embodiment, molar ratio of the epoxy resin to reactive compounds Can be about 1:0.50 to about 1:1.4, about 1:0.60 to about 1:1.3, about 1:0.75 to about 1:1.2 or about 1:0.9 to about 1: 1.10。

(ii) reaction of composition epoxy resin is formed

It is described to react the reaction mixture comprising epoxy resin, the compound comprising cashew nut phenol moieties and reactant from formation Start.Reaction mixture can further include catalyst.In some embodiments, reaction mixture can further include molten Agent.Suitable solvent is known to those skilled in the art.These reactive components can simultaneously, sequentially or with any order add.Epoxy Resin combination can be realized by mixing said components in any of mixing apparatus or reaction vessel.Moreover, with Can be partial or continuous technique in preparing the technique of composition epoxy resin.

In each embodiment, the formation of composition epoxy resin can carry out in the presence of a catalyst.Appropriate catalysts It may include various quaternary phosphine salt catalysts, quaternary ammonium salt, organic proton receptor and inorganic proton acceptor.The non-limiting implementation of quaternary ammonium salt Example may include etamon chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammoinium chloride, Benzyl triethyl ammonium bromide and benzyl triethyl ammonium ammonium iodide.The non-limiting embodiment of organic proton receptor may include imidazoles, benzene And imidazoles, N- methylimidazoles, N- acetyl imidazoles, N- butyl imidazoles, N- benzyl imidazoles, triethanolamine, ethyl dimethylamine, diformazan Amine, diethylamine, dicyclohexyl amine, methyl cyclohexylamine, phenylethylamine, dibenzylamine, methylbenzylamine, ethyl benzyl amine, cyclohexyl aniline, two Butylamine, two tert-butylamines, di-n-propylamine, diamylamine, dicyclohexyl amine, piperidines, pipecoline, 2,5- lupetidines, 2,6- diformazans Phenylpiperidines, piperazine, 2- methyl piperazines, 2,6- lupetazins, morpholine, trimethylamine, triethylamine, diisopropylethylamine, tripropyl amine (TPA), Tri-n-butylamine, 4- methyl morpholines, 4- ethyl morpholines, N- crassitudes, N- methyl piperidines, 1,8- diazabicylos [5.4.0] ten One -7- alkene, pyrazine, 4-dimethylaminopyridine, pyridine, (R)-α-methylbenzyl amine, (S)-α-methylbenzyl amine, α, α-hexichol Base -2- pyrrolidine carbinols (DPP) and α, α-diphenyl -2- pyrrolidine carbinol trimethyl silyl ethers (DPPT).Inorganic proton The non-limiting embodiment of receptor may include sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, cesium carbonate, bicarbonate Sodium, saleratus, sodium carbonate, potassium carbonate, Boratex, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium methoxide, sodium tert-butoxide and tertiary fourth Potassium alcoholate.The non-limiting embodiment of Shi Yi quaternary phosphine catalyst may include benzyltriphenyl phosphonium phosphonium chloride, ethyl San Ben base Yi Suan Phosphonium, second Base triphenyl phosphonium iodide and tetrabutyl Yi Suan Phosphonium.In a preferred embodiment, catalyst can be ethyl triphenyl phosponium acetate Phosphonium.

Epoxy resin to the weight percent of catalyst can according to the type of epoxy resin used, contain cashew nut phenol moieties Type and the reactant of compound and change.In general, epoxy resin can be 0.005 weight % to the weight percent of catalyst To about 2.0 weight %.In each embodiment, epoxy resin can be 0.005 weight % to the weight percent of catalyst To about 2.0 weight %, 0.01 weight % to about 1.75 weight %, 0.05 weight % to about 1.5 weight %, 0.1 weight % to about 1.25 weight % or 0.5 weight % to about 1.0 weight %.

Be commonly used for preparing the reaction of composition epoxy resin at a temperature in the range of can arriving about 200 DEG C at about 100 DEG C into Row.In each embodiment, the temperature of reaction can arrive about 200 DEG C, about 120 DEG C to about 180 DEG C or about 130 DEG C at about 100 DEG C To in the range of about 170 DEG C.In one embodiment, the temperature of reaction can be about 140 DEG C to about 160 DEG C.The reaction Usually carry out under ambient pressure.The reaction can also carry out under an inert atmosphere, such as be carried out under nitrogen, argon or helium.

The duration of the reaction can with and will vary depending on a number of factors, the factor is for example in the process Starting substrates, reaction dissolvent and the temperature used.In general, the duration of the reaction can be at about 5 minutes to about 24 hours In range.In some embodiments, the duration of the reaction can be within the scope of the following：About 5 minutes to about 30 minutes, about 30 minutes to about 2 hours, about 2 hours to about 4 hours, about 4 hours to about 10 hours, about 10 hours to about 15 hours or about 15 are small When by about 24 hours.In preferred embodiments, the reaction can carry out about 2 hours.

(iii) structure and property of composition epoxy resin

As shown in having structure, and it is not limited to the having structure, with lower structure is by epoxy resin, contains There is epoxy resin prepared by the reaction of the reactant of the compound of anacardol and the phenol comprising carboxylic acid and/or with multifunctional hydroxyl General chemical constitution (I)-(IX) of composition (ERC)：

Wherein n can be 1 to 20；

Wherein Z is：

Wherein R⁰For：-C₁₅H_25+2m-

Wherein m can be 0,1,2 or 3.

Wherein R¹For：-C₄H₈-

Wherein R²And R³For：

In addition, in above-mentioned chemical constitution, R⁰Can be 15 carbon atoms containing 0 to 3 carbon-to-carbon double bonds (C=C) Straight chained alkyl, such as R⁰It can be selected from-C₁₅H₃₁、-C₁₅H₂₉、-C₁₅H₂₇With-C₁₅H₂₅；R¹Can have 4 aliphatic structure carbon former Bivalent group (- (the CH of son₂)₄-)；And R²And R³Can be p, the double phenyl structures of p '-isopropylidenes.

In general, composition epoxy resin is at least liquid at 60 DEG C.In addition, composition epoxy resin usually shows at 75 DEG C Viscosity less than about 10,000mPas.In some embodiments, composition epoxy resin is smaller than about in 75 DEG C of viscosity 8,000mPa·s.In other embodiments, composition epoxy resin is smaller than about 6000mPas in 75 DEG C of viscosity.

(b) amino crosslinker compound

Primer coating composition disclosed herein also includes amino crosslinker compound.Amino crosslinker compound can be with It is such as amino resins, etherified amino resins, phenol resin and its mixture.The non-limiting reality of etherified amino crosslinker compound Apply the lower alkyl groups ether that example includes three-, four-, five-and hexamethylolmelamine (alkyl has 1 to 8 carbon atoms) With its mixture.Other non-limiting embodiments of etherified amino resins can be methylated melamine resins, N-butyl Melmac, isobutylated melamine resin, the carbamide resin that methylates, N-butyl carbamide resin, isobutyl carbamide resin Or mixtures thereof.The preferred embodiment that can be used for the amino cross-linking compounds of the present composition may include such as six (methoxies Ylmethyl)-melamine (HMMM) (such as can be obtained from profound new (Allnex) and outside chemical (External Chemical) 's303)。

In general, the weight percent of amino crosslinker compound can be in 4.0 weight % to about 6.0 weight %'s in composition In range.In each embodiment, the weight percent of amino crosslinker compound can be arrived in about 4.0 weight % in composition In the range of about 6.0 weight %, about 4.4 weight % to about 5.6 weight % or 4.8 weight % to about 5.2 weight %.It is excellent at one It selects in embodiment, used epoxy resin can be about 5.0 weight % to the weight ratio of amino crosslinker compound.

(c) optional additive

In each embodiment, primer coating composition can further include it is at least one selected from curing catalysts, it is molten The additive of or mixtures thereof agent, pigment, other additives.

In some embodiments, curing catalysts can be added in the primer coating composition of the present invention to accelerate bottom The solidification process of lacquer coat composition.The non-limiting embodiment of suitable curing catalyst includes three (dimethylaminomethyls)- Phenol, bis- (dimethylaminomethyl)-phenol, salicylic acid, p-methyl benzenesulfonic acid, dinonylnaphthalene disulfonic acid, dinonylnaphthalene sulfonic acid, ten Dialkyl benzene sulfonic acids, bisphenol-A and its mixture.Total weight based on composition, the solidification being included in primer coating composition The amount of catalyst can be in the range of about 0.05 weight % to about 5 weight %.In each embodiment, it is included in primer coating The amount of curing catalysts in composition can be in about 0.1 weight % to about 3 weight % or about 0.2 weight % to about 1 weight %'s In range.

In other embodiments, at least one solvent can be added in primer coating composition to help to reduce combination The viscosity and/or performance parameter of object.The solvent that can be used in composition epoxy resin can be selected from such as ketone, cyclic ketones, ether, fragrance Hydrocarbon, glycol ether and a combination thereof.The non-limiting embodiment of suitable solvent include n-propyl acetate, n-butyl acetate, dimethylbenzene, Ortho-xylene, meta-xylene, paraxylene, (list) propylene glycol (list) methyl ether (PM), acetone, methyl ethyl ketone, methyl tert-butyl Base ketone, ethyl isobutylo ketone, N-Methyl pyrrolidone, dimethylformamide, dimethyl sulfoxide (DMSO) and its mixture.Virtue can also be used Fragrant race's solvent (such as the Solvesso-100 and Solvesso-150 bought from ExxonMobil Chemical) is used as solvent. Generally, based on the total weight of composition, the amount for being included in the solvent in primer coating composition can be in about 5 weight % to about 50 weights In the range of amount %.In each embodiment, the amount of solvent can be that about 5 weight % to 50 weight %, about 10 weight % are arrived About 40 weight % or about 25 weight % to about 35 weight %.

In other embodiments, primer coating composition can further include one or more pigment and/or other can It is used to prepare, stores, applies and cures the additive of primer coating composition.Include filler, leveling auxiliary agent etc. suitable for additive, Or combinations thereof.These optional compounds may include being used to prepare curable composition commonly used in well known by persons skilled in the art Compound in the resin formulation of object and thermosetting object.Generally, based on the total weight of composition, it is included in primer coating composition In pigment and/or the amount of additive can be in the range of about 5 weight % to about 50 weight %.In certain embodiments, face The amount of material and/or additive can be in the range of about 10 weight % be to about 40 weight % or about 25 weight % to about 35 weight %.

(d) formation of primer coating composition

Primer coating composition comprising composition epoxy resin, amino crosslinker compound and optional can be added by formation The reaction mixture of agent is added to prepare.These components can simultaneously, sequentially or with any order add.Reaction mixture can be further Including at least one optional additive.Primer coating composition can be set by the way that said components are blended in any of mixing It is realized in standby or reaction vessel until mixture reaches homogeney.

Be commonly used for preparing the reaction of primer coating composition at a temperature in the range of can arriving about 40 DEG C at about 10 DEG C into Row.In each embodiment, the temperature of reaction can arrive about 30 at about 10 DEG C to about 40 DEG C, about 15 DEG C to about 35 DEG C or about 20 DEG C In the range of DEG C.In one embodiment, the temperature of reaction can be about room temperature (about 23 DEG C).The reaction is usually in environment It is carried out under pressure.The reaction can also carry out under an inert atmosphere, such as be carried out under nitrogen, argon or helium.

The duration of the reaction can with and will vary depending on a number of factors, the factor such as temperature, mixing The amount of method and mixing material.In the range of the duration of the reaction can arrive about 12 hours at about 5 minutes.In some implementations In scheme, the duration of the reaction can be arrived for about 5 minutes to about 30 minutes, about 30 minutes to about 2 hours, about 2 hours About 4 hours, about 4 hours to about 10 hours or about 10 hours to about 12 hours.In each embodiment, preparation can be made to continue straight Until primer coating composition seems to be sufficiently mixed.

(e) property of primer coating composition

In general, primer coating composition is liquid before curing.Primer coating composition disclosed herein is usually opened up Existing low viscosity (<450mPa·s).In each embodiment, primer coating composition can have about 100mPas at about 25 DEG C To the viscosity of about 700mPas.In each embodiment, primer coating composition is about in about 25 DEG C of range of viscosities 100mPas to about 500mPas, about 150mPas are to about 400mPas, about 200mPas to about 350mPas or about 250mPas to about 300mPas.In certain embodiments, at about 25 DEG C, viscosity can be in about 100mPas to about In the range of 300mPas.

In general, primer coating composition may include highly filled (for example, at least 60 weight %).In each embodiment In, the solid that primer coating composition can show about 60 weight % to about 70 weight % or about 62 weight % to about 66 weight % contains Amount.

Primer coating composition disclosed herein usually has low VOC (VOC) concentration (for example, small In about 450g/L).In certain embodiments, the concentration of the volatile organic compounds of primer coating composition can be about 300g/L to about 450g/L.In each embodiment, the concentration of the volatile organic compounds of primer coating composition can be with It is about 330g/L to about 450g/L or about 380g/L to about 420g/L.

As a comparison, the property that is showed of 9 type epoxy resin with including low solid content (<50wt%), high viscosity (> 450mPas) and high volatile organic compound concentrations (>The property of primer coating composition of the present invention 420g/L) is different.

As described herein, primer coating composition can be cured by heating combination.In general, solidification primer coating group In the range of can be arrived at about 100 DEG C by closing the temperature needed for object by about 300 DEG C.In each embodiment, solidification temperature can be about 100 DEG C in the range of about 200 DEG C, about 100 DEG C to about 150 DEG C, about 150 DEG C to about 200 DEG C or about 125 DEG C to about 175 DEG C.In spy Determine in embodiment, solidification temperature can be about 150 DEG C.

Cure primer coating composition duration can with and by according to the type of primer coating composition, temperature, The thickness of humidity and primer coating and change.In general, the duration of solidification primer coating composition can be 5 minutes small to 2 When.In each embodiment, the duration of solidification primer coating composition can be about 5 minutes to 2 hours, about 15 minutes By 1.5 hours or about 30 minutes to 1 hour.In specific embodiments, the duration of solidification primer coating composition can be with It is about 30 minutes.

(II) coated article

The another aspect of the disclosure covers at least part of solidification including adhering at least one surface of substrate or not The article of cured primer coating.The primer coating for adhering to substrate is by that will include composition epoxy resin and amino crosslinking The primer coating composition of immunomodulator compounds is applied to substrate to prepare.In a broad sense, the article may be defined as following material： Wherein primer coating composition is initially applied in and adheres at least part at least one surface of substrate, and wherein priming paint applies Layer can cure under assigned temperature so that primer coating is adhered to substrate.Substrate can be any solidification temperature of bearing with shape At the material of solidify coating.

In each embodiment, substrate can be metal.Substrate as herein defined can be single metal or each The alloy of kind metal.The non-limiting embodiment of these metals include cast iron, aluminium, one-tin brass, steel, copper, allumen, nickel or A combination thereof.In a preferred embodiment, substrate can be steel.

In each embodiment, article can be in various configurations.The non-limiting configuration embodiment of article can be coil, Plate, thin slice, silk thread, pipe or pipeline.The configuration of article can have various sizes, shape, thickness and weight.It is preferably implemented at one In scheme, the shape of article is coil.

Primer coating composition can be applied at least part at least one surface of article, the single surface of article it is complete Portion, article multiple surfaces or side on, on two surfaces of article or each surface of article.In general, can be in a layer Or apply and cure primer coating composition on multiple layers of formation multilayered structure.It in some embodiments, can be on substrate Directly apply and cure primer coating composition.In other embodiments, primer coating composition can be applied to at least one A pretreatment layer.After the solidification of primer coating composition, at least one other coating, such as backing or finishing coat can be applied.

In a preferred embodiment, substrate can be coil.Loop construction may include being coated directly onto on substrate Coil primer coating, such as metal layer.In another embodiment, for example, coil coating structure may include several layers, wherein one A layer is the cured primer coating for adhering to metallic substrate layer, is followed by one or more finishing coats or back sheet.Another Can include several layers between back sheet and finishing coat in embodiment, several layers include (for example) the first primer coating, First pretreatment layer, the first zinc (galvanizing by dipping [HDG]) or zinc-aluminium layer.

As the explaination of the embodiment above, Fig. 1 to Fig. 4 shows each embodiment of coated plate.However, should manage Solution, the present invention is not limited to embodiments shown in attached drawing.

With reference to figure 1, show that the sectional view of the layer structure of 10 instruction of totality number, layered structure include adherency To at least part of primer coating 11 on a surface of substrate (such as metallic plate 12).Primer coating 11 can directly apply simultaneously It adheres on substrate (such as metal layer 12), as shown in fig. 1.It can be as needed by other optional various materials of any amount The bed of material is added in the layer structure of Fig. 1, such as one or more layers between prime coat 11 and metal layer 12.

With reference to figure 2, for example, primer coating structure may include that several layers, one of layer are to adhere to metallic substrate layer 12 Primer coating 11, be followed by one or more back sheets 21.For example, in the embodiment of fig. 2, showing totality number The multilayered structure of 20 instructions comprising the primer coating 11 being clipped between substrate metal plate 12 and backing coating 21.In fig. 2, Show that primer coating 11 adheres at least part on a surface of metallic plate 12, and backing coating 21 adheres to priming paint At least part on 11 surface of coating.Can other optional a variety of materials layers of any amount be added to Fig. 2's as needed One or more layers in layer structure, such as between prime coat 11 and backing coating 21；Or in primer coating 11 and metal One or more layers between layer 12.

With reference to figure 3, another embodiment of the sectional view of the multilayered structure of 30 instruction of totality number, the multilayer are shown Structure includes at least part of first primer coating 31a on a surface for adhering to metallic plate substrate 12；With adhere to At least part of first backing coating 32a of one primer coating 31a.Structure 30 further includes adhere to metallic plate substrate 12 another At least part of second priming coat 31b of one apparent surface；With adhere at least part of the of the first primer coating 31a Two backing coating 32b.Other optional a variety of materials layers of any amount can be added to the layer structure of Fig. 3 as needed In, such as one or more layers between prime coat 31a or 31b and metal layer 12；Or respectively prime coat 31a or 31b with One or more layers between back sheet 32a or 32b.

With reference to figure 4, it is commonly used for preparing other layers of final products (for example, multilayered structure of logical commonly used digital 40 instruction) It may include for example through respective pretreatment the first zinc layers 42a and the second zinc layers 42b the first pretreatment layer 41a being respectively formed and Two pretreatment layer 41b.First zinc layers 42a and the second zinc layers 42b may include the top surface for for example adhering to metal substrate 12 respectively At least part and bottom surface at least part (i.e. two surfaces) zinc layers (galvanizing by dipping [HDG]) or zinc-aluminium layer.Zinc Layer 42a and 42b adheres to the surface of pretreatment layer 41a and 41b respectively.In the embodiment depicted in fig. 4, prime coat 31a and 31b adheres to pretreatment layer 41a and 41b respectively.Back sheet 32a and 32b adhere to prime coat 31a and 31b respectively.Back sheet 32a is commonly referred to as " finishing coat ", because this side of loop product 40 is typically applied to be directly facing sunlight in final products Top side on；And back sheet 32b is commonly referred to as " backing ", because this side of loop product 40 is typically applied to finally producing Product 40 deviate from sunlight or the back side opposite with sunlight.It can be as needed by other optional various materials of any amount The bed of material is added in the multilayered structure of Fig. 4, such as one between back sheet 32a or 32b and prime coat 31a or 31b respectively Or multiple layers；Or one or more layers between zinc layers 42a or 42b and metal layer 12 respectively.

In each embodiment, cured paint base composition can show the crosscutting adhesion strength of height of 3B to 5B.In other realities It applies in scheme, crosscutting adhesion strength in the range of 3B to about 5B, about 4B to about 5B or can be more than 5B.In certain embodiments In, crosscutting adhesion strength can be about 5B.

Pencil hardness is the measurement of solidify coating hardness.In general, cured primer coating can show the high lead from HB to 3H Hardness.In each embodiment, pencil hardness can from HB to about 3H, from about F to 2H or from 1H to 2H in the range of.

In each embodiment, cured primer coating can be presented within the scope of about 50kg.cm to about 100kg.cm High resistance to reverse impact.In each embodiment, resistance to reverse impact can in about 50kg.cm to about 100kg.cm, about In the range of 60kg.cm to about 90kg.cm or about 70kg.cm to about 80kg.cm.

Another valuable measurement of solidify coating is that the bending of T shapes is flexible.In general, cured primer coating can show from 0T to The high T shapes bending of 2T is flexible.In each embodiment, T shapes are bent flexibility can be in the range of 0T be to about 1T or 1T to about 2T.

In each cured primer coating, methyl ethyl ketone (MEK) tolerance is show coating chemical resistance another Measurement.It in certain embodiments, can be in the range of 5 double frictions to 100 double frictions with the MEK tolerances of double rub measurements It is interior.In other embodiments, MEK tolerances can about 5 times to 100 times double frictions, about 10 times to 90 times double frictions, about 25 times To in the range of 75 double frictions or 40 times to 60 times double frictions.

Another measurement of these cured primer coating compositions is thickness of dry film (DFT).In each embodiment, Gu The primer film of change has at 0 micron to the DFT in about 15 micron ranges.In certain embodiments, DFT can be arrived at about 0 micron In the range of 15 microns, about 2.5 microns to 12.5 microns, about 5 microns to 10 microns or about 6 microns to 8 microns.

The critical nature that cured primer coating is showed is corrosion resistance.In the solidification with salting liquid spraying scribing line Primer coating after measure this corrosion resistance.After a period of time, film is assessed before and after being exposed to salting liquid Surface nature.Compared with other business coatings, the measurement usually obtained is creep value.In each embodiment, this hair The creep value of the solidification primer coating of bright middle scribing line can be 3mm to about 5mm.In each embodiment, creep value can be in 3mm To in the range of 4mm or 4mm to 5mm.As a comparison, business coating has the creep value of 8mm to 11.5mm.Fig. 5 to Fig. 8 is shown The comparison of solidify coating composite of the salt spray test before and after 7 days.

(III) technique for preparing cured primer coating

Another aspect of the present disclosure provides the technique for preparing cured primer coating.The technique includes providing to exist above The curable primer coating composition being partly described in detail in (I), and curable primer coating composition is heated to about 100 DEG C and is arrived 300 DEG C of temperature is to form cured primer coating.In general, before the heating stepses of the technique, by curable priming paint Coating composition is applied at least part of article surface to be coated.

(a) curable coating composition is provided

Above suitable curable primer coating composition is described in part (I).

(b) primer coating composition is applied

The technique further comprises for curable primer coating composition being applied to the one of at least one surface of substrate Part.Above appropriate substrate is detailed in part (II).The application of curable primer coating composition can pass through various means To apply.For example, drawdown rod, roller, knife, paintbrush, sprayer, dip-coating or its other party well known by persons skilled in the art can be used Method applies primer coating composition.Moreover, laminated coating can be formed using the primary above application of primer coating composition. As set forth in detail above, curable primer coating composition can be applied to one or more surfaces of article to be coated.

(c) it heats and primer coating composition can be cured

The technique further comprise by curable primer coating composition be heated to about 100 DEG C to 300 DEG C of temperature with Form cured primer coating.In one embodiment, curable primer composition of the invention is curable to form thermosetting Property or solidification composition filling.For example, the curable primer composition of the present invention can be cured to form film under Conventional processing conditions, apply Layer or solid.Cure curable paint base composition can carry out being enough to cure under the cured reaction condition including predetermined temperature The predetermined amount of time of composition.In general, primer coating composition can be heated to about 100 DEG C to about 300 DEG C of temperature, to be formed Cured primer coating.In each embodiment, primer coating composition can be heated to about 100 DEG C to about 200 DEG C, about 100 DEG C to about 150 DEG C, about 150 DEG C to about 200 DEG C or about 125 DEG C to about 175 DEG C of temperature.In specific embodiments, cure Temperature can be about 150 DEG C.Method for heating substrate can by conventional methods or the method that passes through those skilled in the art It carries out.In general, the duration of heating stepses can be 5 minutes to 2 hours.In each embodiment, heating stepses are held The continuous time can be about 5 minutes to 2 hours, about 15 minutes to 1.5 hours or about 30 minutes to 1 hour.In particular implementation In, the duration of heating stepses can be about 30 minutes.

(d) property of cured primer coating

After the solidification of primer coating composition, the cured primer coating of gained can show several beneficial physical properties. In each embodiment, the cured primer coating of gained shows following property：Including such as high-adhesiveness, high pencil hardness, High resistance to reverse impact, high T shapes bending flexibility, acceptable MEK tolerances.

Another valuable measurement of solidify coating is that the bending of T shapes is flexible.It is arrived in general, cured primer coating can be presented in 0T High T shapes bending within the scope of 3T is flexible.In each embodiment, the bending of T shapes is flexible can be in 0T to about 1T or 1T to about 2T's In range.

Another measurement of these cured primer coating compositions is thickness of dry film (DFT).In each embodiment, Gu The primer film of change has at 0 micron to the DFT in about 15 micron ranges.In certain embodiments, DFT can be arrived at about 0 micron 15 microns, about 2.5 microns to 12.5 microns, in the range of about 5 microns of microns to 10 microns or about 6 microns to 8 microns.

Definition

When introducing the element of embodiment described herein, article " one (a, an) ", " (the and the said) " are intended to There are one or more elements for expression.Term " include (comprising) ", " including (including) " and " have (having) " it is intended to inclusive, and means that other element also may be present other than listed element.

Term " alkyl " as used herein describes the saturated hydrocarbyl containing 1 to 30 carbon atoms.They can be straight chain, Have branch or it is cricoid, can be substituted as defined below, and include methyl, ethyl, propyl, isopropyl, butyl, oneself Base, heptyl, octyl, nonyl etc..

Term " hydrocarbon " and " alkyl " as used herein describe the organic compound or group being only made of elemental carbon and hydrogen. These parts include alkyl, alkenyl, alkynyl and aryl moiety.These parts further include being replaced by other aliphatic or cyclic hydrocarbon group Alkyl, alkenyl, alkynyl and aryl moiety, such as alkaryl, alkene aryl and alkynes aryl.They can be straight chain, tool branch Or it is cricoid.Unless otherwise instructed, otherwise these parts preferably comprise 1 to 20 carbon atoms.

" substituted alkyl " as described herein is partly the hydrocarbyl portion of the atom substitution in addition to carbon through at least one, The part that is replaced by hetero atom (such as nitrogen, oxygen, silicon, phosphorus, boron or halogen atom) including wherein carbon chain atom and wherein carbochain includes The part of other substituent groups.These substituent groups include alkyl, alkoxy, acyl group, acyloxy, alkenyl, alkenyloxy group, aryl, fragrant oxygen Base, amino, amide groups, acetal, carbamyl, carbocyclic ring, cyano, ester, ether, halogen, heterocycle, hydroxyl, ketone group, ketal, phosphorus base, nitre Base and sulfenyl.

The present invention is described in detail, it is obvious that the present invention's defined without departing substantially from appended claims In the case of range, it can modify and change.

Embodiment

Following embodiment and comparing embodiment further illustrate each embodiment of the present invention in detail, but it should not be understood To limit the scope of the invention.Unless otherwise directed, otherwise all parts and percentages are all by weight.It is retouched in following table I State various terms, title and the material used in following embodiment.

Table I-raw material

Canonical measure, analytical equipment and method used in embodiment is as follows：

Viscosity

Viscosity is according to the entitled " standard testings of transparent and opaque liquid kinematic viscosity of ASTM D445 (2010) Method (and calculating of dynamic viscosity) (Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity)) " method, It is measured using the Brookfield CAP-2000+ with No. 6 axis.

Epoxide equivalent (EEW)

EEW is by using Mettler Toledo T70Titrator according to ASTM D1652 (2004) entitled " ring Standard method of test (the Standard Test Method for Epoxy Content of of the epoxy content of oxygen resin Epoxy Resins) " test method measure.

Decomposition temperature (Td)

T_dBe using TA Instruments TGA Q50 according to IPC-TM-650 (2006) it is entitled " laminated material Decomposition temperature (T_d) (TGA methods) (Decomposition Temperature (T_d)of Laminate Material Using TGA method) " measures.

Film thickness

Thickness of dry film is measured and is averaging using 4500 elcometers of BYKO manufactured by BYK.

The bis- frictions of solvent resistance-

" standard practices (Standard of the solvent resistance of solvent friction assessment organic coating is used according to entitled Practice for Assessing the Solvent Resistance of Organic Coatings Using Solvent Rubs) " ASTM D5402 (2006), measure solvent resistance using methyl ethyl ketone (MEK).When observing film Degradation or layering when, record double Rubbing numbers.

Pencil hardness

Pencil hardness is entitled " by the standard survey for the film hardness that pencil test carries out according to ASTM D3363 (2005) The test method of method for testing (Standard Test Method for Film Hardness by Pencil Test) " is surveyed Amount.The measuring scale of hardness 6B it is (softer) to 6H (harder) in the range of.

The bending of T shapes is flexible

T shapes bending flexibility is according to ISO17132 (2007) entitled " paint and varnish-T shape crooked tests (Paints And Varnishes-T-Bend Test) " method measure.T shapes are bent measuring scale flexible and arrive 4T in 0T (high flexibility) In the range of (difference is flexible).

Cross-hatched adhesion strength

The cross-hatched adhesion strength of coating is " standard method of test of adhesion strength to be measured by adhesive tape test according to entitled The ASTM D3359 of (Standard Test Methods for Measuring Adhesion by Tape Test) " (2009) program described in measures and standard described in described program is evaluated.Cross-hatched adhesion strength Measuring scale 5B (excellent adhesion) arrive 0B (poor adhesion strength) in the range of.

Impact resistance

The resistance to reverse impact of cured film is according to entitled " the standard survey of the resistance to effect of rapid deformation of organic coating (impact) Method for testing (Standard Test Method for Resistance of Organic Coatings to the Effects Of Rapid Deformation (Impact)) " ASTM D2794-93 (2010) measure.The measuring scale of impact resistance <1kgcm (frangible) is arrived>In the range of 100kgcm (flexibility).

Corrosion resistance is tested

Salt spray test is carried out to assess dry-coated tunic according to the ASTM B117-03 standard practices of operation salt fog (mist) device Corrosion resistance.It after solidification, with tape-stripping coating panel and crosses, is then placed in salt spray chamber with molten in 5wt%NaCl Exposure in liquid.The exposed region of salt spray chamber maintains about 35 DEG C.Salt spray test is carried out continuously 7 days.Measure scribing line creep rate (creep away from From) to be assessed.

Prepare the general procedure of composition/cured product

Prepare curable compositions and using the composition cured product to be typically prepared program as follows：By CNSL, There are two the phenol of hydroxyl and epoxy resin to be loaded into the reactor with mechanical agitator for dicarboxylic acids or tool, and is heated to foot To maintain reaction mixture to be in the temperature of stable condition, such as it is up to about 90 DEG C of equilibrium temperature.Then by catalyst (such as Ethyl San Ben base Yi Suan Phosphonium catalyst) it is added in reactor and is mixed with the other compositions in reactor.Make in next step Temperature in reactor is increased to the reaction temperature for being enough drive response mixture, for example, about 140 DEG C to about 170 DEG C of reaction temperature Degree.Reaction mixture (such as with 10 DEG C/2 minutes rate) is slowly heated to reach reaction temperature；Then in certain solidification Between after section, such as after about 2 hours reaction time, stop reaction.

Synthetic example 1：The preparation of composition epoxy resin (ERC1)

By 720.0g D.E.R.383^TMEpoxy resin, 43.8g adipic acids and 453.0g cashew nut shell oils (CNSL) are loaded into and match It has in four neck glass flasks of mechanical agitator, condenser pipe and nitrogen charging connector.The gained mixture being slowly heated in flask. After so that the temperature of mixture is slowly raised 130 DEG C, the temperature is kept constant 10 minutes (min).Then, by 500ppm ethyls San Ben base Yi Suan Phosphonium (70% methanol solution) is loaded into flask.The temperature of gained reaction mixture is set to be slowly raised 160 ℃.The EEW of reaction mixture is monitored during reaction.2 hours (hr) stops reaction afterwards.Products therefrom (is referred to herein as " ERC1 ") be revealed as clarification and it is sticky, and with 1,068 (g/eq) EEW.

Synthetic example 2：The preparation of resin combination (ERC2)

By 480.0g D.E.R.383^TMEpoxy resin, 45.6.g bisphenol-As and 307.6g CNSL are loaded into equipped with machinery In four neck glass flasks of blender, condenser pipe and nitrogen charging connector.The gained mixture being slowly heated in flask.Make mixture Temperature be slowly raised 130 DEG C after, the temperature is kept constant 10 minutes.Then, by 500ppm ethyl San Ben base Yi Suan Phosphonium (70% methanol solution) is loaded into flask.The temperature of gained reaction mixture is set to be slowly raised 160 DEG C.During reaction Monitor the EEW of reaction mixture.Stop reaction after 2hr.Products therefrom (being referred to herein as " ERC2 ") be revealed as clarification and it is sticky, And the EEW with 990 (g/eq).

Synthetic example 3：The preparation of epoxy resin composition (ERC3)

By 480.0g D.E.R.383^TMEpoxy resin, 112.2g dimer (fatty acid) yls and 307.6g CNSL be loaded into equipped with Mechanical agitator, condenser pipe, nitrogen charging adapter four neck glass flasks in.The gained mixture being slowly heated in flask.Make After the temperature of mixture is slowly raised 130 DEG C, the temperature is kept constant 10 minutes.Then, by 500ppm ethyl triphenyls Yi Suan Phosphonium (70% methanol solution) is loaded into flask.The temperature of gained reaction mixture is set to be slowly raised 160 DEG C.Anti- The EEW of monitoring reaction mixture during answering.Stop reaction after 2hr.Products therefrom (being referred to herein as " ERC3 ") is revealed as clarifying And it is sticky, and the EEW with 1,185 (g/eq).

Table II shows synthetic example 1 (ERC1), synthetic example 2 (ERC2) and synthetic example 3 (ERC3) asphalt mixtures modified by epoxy resin Fat and solid epoxy (SER):D.E.R.671^TMSeveral properties that (1 type epoxy resin and business epoxy product) compares. " 1 type " to " 9 type " epoxy resin is epoxy resin industry essential term, and the molecular weight (MW) based on epoxy resin describes ring Oxygen resin.ERC1, ERC2 and ERC3 are in a liquid state at 75 DEG C, and viscosity is respectively 8025mPas, 8,250mPa s and 6, 150mPa·s；And SERD.E.R.671 is still in solid-state at 75 DEG C.As shown in table it, the ratio of viscosities of ERC1, ERC2 and ERC3 D.E.R.671^TMEpoxy resin is low.Moreover, advantageously, ERC1, ERC2 and ERC3 show higher T_d。

The Nature comparison of Table II-epoxy resin

* NA=is not applicable

Embodiment 1-3 and comparing embodiment A and B-priming paint composite

In these embodiments, first group of coil primer coating composite is prepared, and by the property of this type coating composite Matter is compared to each other.Use ERC components (a) (i.e. synthetic example 1 (ERC1), synthetic example 2 (ERC2) and synthetic example 3 (ERC3)) the coil priming paint of the present invention including embodiment 1 (F-1), embodiment 2 (F-2) and embodiment 3 (F-3) is prepared Coating composite.Other than above-mentioned ERC, commercial polyesters polyol resin (Dynapol LH818-05 polyester) and business are used Epoxy resin D.E.R.669 epoxy resin carrys out production line circle primer coating composite as comparing embodiment.Comparing embodiment A (F-A) it is the coating composite for using LH 818-05 polyester；And comparing embodiment B (F-B) be LH 818-05 polyester and The admixture of DER669.By each and six as component (b) amino crosslinker in above-mentioned epoxy resin and polyester resin (methoxy) melamine (Cymel 303) is deployed into coil primer coating composite together.Table III describes F-1 and arrives Each in the primer coating composite of F-3 (embodiment 1-3) and F-A and F-B (being respectively comparing embodiment A and B).

Compare the composite property as described in Table III, the composite with ERC, F-1 to F-3 shows lower viscosity With lower VOC content, and ERC composites reach than F-A (polyester) and F-B (669 epoxy admixtures of polyester/DER) is high consolidates Body content.

Table III-primer coating composite and property

Described in Table III as above, by the viscosity number of composite F-1 to F-3 (embodiment 1-3) and comparing embodiment A (F-A) and The coil primer coating composite of comparing embodiment B (F-B) is compared.Each composite is prepared to show similar viscosity, However the comparison composite (F-A and F-B) containing polyester polyol need using high VOC content (such as>530g/L).Compared to it Under, ERC of the invention (i.e. F-1, F-2 and F-3 containing epoxy resin) uses low VOC content (such as 420g/L).

Embodiment 4-6 and comparing embodiment C and D-primer coating

Primer coating (i.e. film) is prepared by the above-mentioned primer coating composite described in upper Table III.For prepares coating film, By with pull rod on black sheet iron Coating film, coil primer coating composite is poured into black sheet iron (black sheet iron Size is 10cm × 15cm and 0.05cm thick) on, then applied by toasting black sheet iron coating 30 minutes at 150 DEG C to cure Tunic.Then, the property of gained membrane coat is measured.The performance of the primer coating of each preparation is assessed, and result is described in table In IV.As shown in Table IV, the property of the primer coating made of ERC show with other comparable adhesivenesses of comparison primer coating, Impact resistance and the bending of T shapes are flexible.The hardness and MEK tolerances of the priming paint are weaker than other priming paint.

Table V-primer coating property

Embodiment 7 and 8 and comparing embodiment E and G

Part A：Prepare the general procedure of coil primer coating composite

In these embodiments, second group of coil primer coating composite is prepared, and by the property of this type coating composite Matter is compared to each other.In preparing one embodiment of coil primer coating composite (F-7) of the embodiment of the present invention 1, ERC is used Component (a), i.e. synthetic example 1 (ERC1)；And in the coil primer coating composite (F-8) for preparing the embodiment of the present invention 2 Another embodiment in, ERC I and commercial epoxy resin DER 669 are applied in combination.

Other than above-mentioned ERC resins, the coil as comparing embodiment is prepared using commercial epoxy resin DER 669 Primer coating composite comparing embodiment E (F-E)；And (Dynapol LH 818-05 are poly- using commercial polyesters polyol resin Ester) produce the coil primer coating composite comparing embodiment G (F-G) as comparing embodiment.

Each in above-mentioned resin is deployed into the allotment of coil primer coating together with amino crosslinker (Cymel 303) Object.Table V describes every in primer coating composite F-7 and F-8 of the present invention and the comparison composite F-E and F-G that are prepared as above A kind of and each composite component.The property of coil primer coating composite is also measured, and is described in table V.

Compare the property of composite, the composite (F-7 and F-8) with ERC1 shows lower viscosity and lower VOC Content, and the composite with ERC1 realizes higher solid content.In contrast, containing DER 669^TMComposite (F-E and F-G it) shows highest viscosity, while there is minimum solid content.

Table V-primer coating composite and property

Part B：Prepare the general procedure of coil primer coating

It is prepared by the above-mentioned primer coating described in upper Table V using general procedure part B as described in Example 1 Object prepares coil primer coating (i.e. film).

The performance of the primer coating of each preparation is assessed, and result describes in Table VI.As shown in Table VI, it is prepared by ERC1 Primer coating (F-7) in adhesiveness, hardness, impact resistance, the bending of T shapes be flexible and all properties of MEK tolerances all Show good nature, and by DER 669^TMThe T shapes bending that primer coating (F-E) prepared by epoxy resin shows difference is flexible.T shapes are curved Bent flexibility is the very important property of coating, and the coating is enable to be used for coil coating application.

The coated film prepared by the composite (F-E) with 669 epoxy resin of DER or the composite (F-G) with polyester With undesirable property.The primer coating prepared by ERC1 shows the hardness number lower than other coated films.

It is assumed that being provided for primer coating due to the special chemical structure of the ERC1 used in primer coating of the invention The flexibility of improvement.The composite (F-E) of DER 669 shows higher hardness, but it is flexible (3T) to show very weak T shapes bending.

Table VI：Primer coating property

Salt spray test

The anti-corrosive properties that coating is showed are the key properties of coil primer coating application.Salt fog survey is carried out to solidify coating film Examination.Fig. 5 to Fig. 8 is the photo of the coated film shot before and after salt spray test.Each of Fig. 5 to Fig. 8 schemes Three individual image A-C, described image are shown：(A) there is the original coated film of scribing line before salt spray test；(B) salt fog Coated film after test；(C) scrapes the coated film of the creep value (distance) to measure corrosion along scribing line.

All coated films all show red rust on the surface far from scribing line.With the composite F-7 phases of the present invention with ERC1 Than the coated film prepared by the comparison composite F-G with polyester shows most intensive rust mark.It is corrosion-damaged to occur (as being bubbled) In the scribe area of each coated film.The creep value (most wide corrosion length) along scribing line is compared, and result is listed in Table VII In.The embodiment of composite F-7 of the present invention have 3.60 creep value, and compare composite F-E and F-G show 11.27mm and The severe creep deformation distance of 8.98mm.

Anticorrosive property is the critical nature of primer coating.As shown in Table VII primer coating, F-7 is being drawn after salt spray test Line region shows the much better corrosion resistance of comparison primer coating than F-E and F-G, i.e., lower creep value.

Anti-corrosive properties confrontation is most important in the application of coil priming paint.To the solidify coating film and commercial sample of F-6 to F-9 (curing 30 minutes at 150 DEG C) carries out salt spray test, and continues 7 days.Fig. 1-5 is shot before and after salt spray test Coated film photo.Each figure includes three images：There is the original coated film of scribing line before salt spray test；In salt spray test Coated film afterwards；The coated film of the creep(ing) distance to measure corrosion is scraped along scribing line.

All coated films all show red rust on the surface far from scribing line.With 6 phase of composite with neo-epoxy resin Than the composite 8 with polyester shows most intensive rust mark.The corrosion-damaged drawn area that each coated film is appeared in (as being bubbled) Domain.The creep value (most wide corrosion length) along scribing line is compared, and the results are shown in Table 9.With neo-epoxy resin Composite 6 has 3.60 creep value, this is suitable with business composite.Composite 7 and 8 shows serious creep(ing) distance 11.27 And 8.98mm.This result shows that the priming paint composite with neo-epoxy resin with good corrosion resistance.

Table VII：The anti-corrosion property of salt spray test：

Property	F-7	F-E	F-G	F-8	Commercially
						Scribing line distance after test	3.60	11.27	8.98	4.64	2.52

Claims

1. a kind of coating composition, the composition include：

(a) composition epoxy resin of a concentration of about 25 weight % to about 35 weight %；With

(b) amino crosslinker compound.

2. coating composition as described in claim 1, wherein the reaction that the composition epoxy resin includes the following terms is produced Object：(i) epoxy resin, the compound of (ii) containing cashew nut phenol moieties and (iii) are selected from or mixtures thereof carboxylic acid, phenolic compound Reactant.

3. coating composition as claimed in claim 1 or 2 is less than about wherein the composition epoxy resin has at 75 DEG C The viscosity of 10,000mPas.

4. the coating composition as described in any one of Claim 1-3, wherein the amino crosslinker compound is etherificate ammonia Base resin.

5. coating composition as claimed in claim 4, wherein the etherified amino resins be selected from methylated melamine resins, N-butyl melmac, isobutylated melamine resin, the carbamide resin that methylates, N-butyl carbamide resin, isobutyl group Change or mixtures thereof carbamide resin.

6. the coating composition as described in any one of claim 1 to 5, wherein the amino crosslinker compound has about 4 Concentration of the weight % to about 6 weight %.

7. the coating composition as described in any one of claim 1 to 6 further includes at least one selected from the following terms Additive：Or mixtures thereof curing catalysts, solvent, pigment.

8. the coating composition as described in any one of claim 1 to 7, wherein the composition shows about 60 weight % to about The solid content of 70 weight %.

9. the coating composition as described in any one of claim 1 to 8 is less than about wherein the composition shows at 25 DEG C The viscosity of 450mPas.

10. the coating composition as described in any one of claim 1 to 9, wherein the composition have be less than about 450 grams/ The volatile organic compounds concentration risen.

11. the coating composition as described in any one of claim 1 to 10, wherein the composition is by being heated to about 100 DEG C to about 300 DEG C of temperature and cure.

12. a kind of method preparing solidify coating, the method includes：

(i) curable coating composition is provided, the curable coating composition includes (a) about 25 weight % to about 35 weight % Composition epoxy resin and (b) amino crosslinker compound；With

(ii) curable coating composition is heated to about 100 DEG C to about 300 DEG C of temperature to form the solidify coating.

13. method as claimed in claim 12, wherein the composition epoxy resin includes the reaction product of the following terms： (i) epoxy resin, the compound of (ii) containing cashew nut phenol moieties and (iii) are selected from or mixtures thereof carboxylic acid, phenolic compound Reactant.

14. method as described in claim 12 or 13, wherein the composition epoxy resin has at 75 DEG C is less than about 10, The viscosity of 000mPas.

15. the method as described in any one of claim 12 to 14, wherein the amino crosslinker compound is selected from following Every etherified amino resins：Methylated melamine resins, N-butyl melmac, isobutylated melamine tree Or mixtures thereof fat, the carbamide resin that methylates, N-butyl carbamide resin, isobutyl carbamide resin.

16. the method as described in any one of claim 12 to 15, wherein in the curable coating composition, the ammonia Based cross-linker compound has the concentration of about 4 weight % to about 6 weight %.

17. the method as described in any one of claim 12 to 16, wherein the curable coating composition further includes At least one additive selected from the following terms：Or mixtures thereof curing catalysts, solvent, pigment.

18. the method as described in any one of claim 12 to 17, wherein the curable coating composition shows about 60 weights It measures the solid content of % to about 70 weight % and is less than about the viscosity of 450mPas at 25 DEG C.

19. the method as described in any one of claim 12 to 18, wherein before the heating stepses, it will be described curable Coating composition is applied at least part of substrate surface.

20. method as claimed in claim 19, wherein the substrate is metal.

21. the method as described in any one of claim 12 to 20, wherein the solidify coating shows the T shapes of about 0T to about 2T Bending is flexible.

22. the method as described in any one of claim 12 to 21, wherein the solidify coating shows corrosion resistance, it is described resistance to Corrosivity is measured to the creep value of about 5mm with about 3mm in scribe area.

23. a kind of article, the article includes substrate and adheres at least part of coating of the substrate surface, wherein institute Stating coating is prepared by applying coating composition, and the coating composition includes (a) about 25 weight % to about 35 weight % Composition epoxy resin and (b) amino crosslinker compound.

24. article as claimed in claim 23, wherein the substrate is metal.

25. the article as described in claim 23 or 24, wherein the reaction that the composition epoxy resin includes the following terms is produced Object：(i) epoxy resin, the compound of (ii) containing cashew nut phenol moieties and (iii) are selected from or mixtures thereof carboxylic acid, phenolic compound Reactant.

26. the article as described in any one of claim 23 to 25, wherein the composition epoxy resin have at 75 DEG C it is small In the viscosity of about 10,000mPas.

27. the article as described in any one of claim 23 to 26, wherein the amino crosslinker compound is selected from following Every etherified amino resins：Methylated melamine resins, N-butyl melmac, isobutylated melamine tree Or mixtures thereof fat, the carbamide resin that methylates, N-butyl carbamide resin, isobutyl carbamide resin.

28. the article as described in any one of claim 23 to 27, wherein in the coating composition, the amino crosslinking Immunomodulator compounds have the concentration of about 4 weight % to about 6 weight %.

29. the article as described in any one of claim 23 to 28, wherein the coating is by being heated to about 100 DEG C to about 300 DEG C of temperature is adhered to the substrate.

30. article as claimed in claim 29, wherein the T shapes bending that the coating shows about 0T to about 2T is flexible.

31. the article as described in claim 29 or 30, wherein the coating shows corrosion resistance, the corrosion resistance is to draw About 3mm is measured to the creep value of about 5mm in line region.

32. the article as described in any one of claim 23 to 31 further comprises at least one other coating.