CN1075727A - Modified epoxy resin composition, the coating composition of curable compositions and low gloss - Google Patents
Modified epoxy resin composition, the coating composition of curable compositions and low gloss Download PDFInfo
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- CN1075727A CN1075727A CN93102369A CN93102369A CN1075727A CN 1075727 A CN1075727 A CN 1075727A CN 93102369 A CN93102369 A CN 93102369A CN 93102369 A CN93102369 A CN 93102369A CN 1075727 A CN1075727 A CN 1075727A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
- C08G59/1422—Polycondensates modified by chemical after-treatment with inorganic compounds containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Resins (AREA)
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Abstract
Composition epoxy resin contains the carbonyl bearing polymer as low gloss additives, owing at least a stabilizer compounds that adds stable quantity become store more stable, these compounds are organic carboxylates of (a) at least a periodic table of elements IA, IIA, IIB, IIIA, VIB or VIII family metal, (b) at least a zinc carbonate, zinc oxide, yellow soda ash or salt of wormwood; Or (c) (a) and any combination (b).This composition is particularly suitable for the application in the powder coating.
Description
The present invention relates to the low coating composition of modified epoxy resin composition, curable compositions and gloss.
The epoxy resin-matrix powder coating has higher gloss usually, in some applications, wishes glossy low coating.Importantly fill a prescription, this prescription not only provides gloss low coating, but also makes coating formulation gloss in the required storage time stable.
Davis is at US4, discloses a class coating composition in 419,495, comprise a kind of Resins, epoxy and at least as solidifying agent part usefulness contain can with a kind of polymkeric substance of Resins, epoxy reactive group.These coating compositions it is said to have low gloss.Although these coating have low gloss really, this coating composition has the short storage time.This that is to say that the coating composition storage time is long more, and the gloss of gained coating is strong more.The low gloss here be with a kind of like this gloss of coating relatively, this coating contains the epoxy substituting group but does not contain any can preparation with the multipolymer of the group of Resins, epoxy radical reaction from being similar to.
Therefore wish to have a kind of suitable modified epoxy resin composition, said composition includes a kind of polymkeric substance, the group of this polymkeric substance can react with epoxide group, and when being mixed with coating composition, this coating composition has improved the stability in storage of gained coating gloss.
On the one hand, the present invention relates to the improvement to modified epoxy resin composition, said composition comprises:
(A) at least a Resins, epoxy, this Resins, epoxy contain per molecule on average more than an ortho position epoxy group(ing), and have an aromatic ring on its main chain at least; With
(B) at least a polymkeric substance, this polymkeric substance is by one or more ethylenically unsaturated monomers preparations, at least a hydroxy-acid group that contains in these monomers;
Its improvement is to have added in the said composition
(C) stabilizer compounds of at least a stable quantity, it is:
(a). the organic carboxylate of at least a periodic table of elements I A, II A, II B, III A, VI B or VIII family metal;
(b). at least a zinc carbonate, zinc oxide, yellow soda ash or salt of wormwood; Or
.(a) and (b) any combination (c).
The present invention relates to be suitable for the improvement as the composition of epoxy curing agent on the other hand, said composition comprises:
(1) at least a polymkeric substance, this polymkeric substance is by one or more ethylenically unsaturated monomers preparations, at least a hydroxy-acid group that contains in these monomers; With
(2) at least aly be used for described curing agent for epoxy resin, this solidifying agent is different from component (1);
Wherein said improvement is to have added in described curing agent composition:
(a). the organic carboxylate of at least a periodic table of elements I A, II A, II B, III A, VI B or VIII family metal;
(b). at least a zinc carbonate, zinc oxide, yellow soda ash or salt of wormwood; Or
.(a) and (b) any combination (c).
The present invention relates to the improvement of curable compositions more on the one hand, said composition comprises:
(A) at least a Resins, epoxy contains average per molecule more than an ortho position epoxy group(ing), and has an aromatic ring on its main chain at least; With
(B) at least a polymkeric substance is by one or more ethylenically unsaturated monomers preparations, at least a hydroxy-acid group that contains in these monomers;
(D) be used for the solidifying agent of at least a curing amount of component (A), it both had been different from component (B) and also had been different from component (B) and pre-reaction product (C);
Wherein said improvement is to have added in the described composition:
(C) stabilizer compounds of at least a stable quantity, it is:
(a). the organic carboxylate of at least a periodic table of elements I A, II A, II B, III A, VI B or VIII family metal;
(b). at least a zinc carbonate, zinc oxide, yellow soda ash or salt of wormwood; Or
(c). any (a) and (b) combination.
Another aspect the present invention relates to the improvement of powder paint compositions, and said composition contains the pigment or the filler of obvious amount, and it comprises:
(A) at least a Resins, epoxy contains average per molecule more than an ortho position epoxy group(ing), and has an aromatic ring in its main chain at least;
(B) at least a polymkeric substance is by one or more ethylenically unsaturated monomers preparations, at least a hydroxy-acid group that contains in these monomers;
(D) at least a solidifying agent that is used for the curing amount of component (A), it both had been different from component (B) and also had been different from component (B) and pre-reaction product (C);
(E) at least a or multiple interpolation component that is selected from flow control agent, homogenizing auxiliary agent, promotor or catalyzer;
Wherein said improvement is to have added in the described composition:
(C) stabilizer compounds of at least a stable quantity, it is:
(a). the organic carboxylate of at least a periodic table of elements I A, II A, II B, III A, VI B or VIII family metal;
(b). at least a zinc carbonate, zinc oxide, yellow soda ash or salt of wormwood; Or
(c). arbitrary (a) and (b) combination.
The present invention further also relates to the improvement of the powder paint compositions of essentially no pigment and filler, and said composition comprises:
(A) at least a Resins, epoxy contains average per molecule more than an ortho position epoxy group(ing), and has an aromatic ring in its main chain at least;
(B) at least a polymkeric substance is by one or more ethylenically unsaturated monomers preparations, at least a hydroxy-acid group that contains in these monomers;
(D) at least a solidifying agent that is used for the curing amount of component (A), it both had been different from component (B) and also had been different from component (B) and pre-reaction product (C); With
(E) at least a or multiple interpolation component that is selected from flow control agent, homogenizing auxiliary agent, promotor or catalyzer;
Wherein said improvement is to have added in the described composition:
(C) stabilizer compounds of at least a stable quantity, it is:
(a). the organic carboxylate of at least a periodic table of elements I A, II A, II B, III A, VI B or VIII family metal;
(b). at least a zinc carbonate, zinc oxide, yellow soda ash or salt of wormwood; Or
(c). arbitrary (a) and (b) combination.
The present invention further also relates to solidifies the product that the foregoing curable composition obtains.
The present invention further also relates to the goods with the aforementioned coating composition coated.
The present invention can suitably contain or it consists of or it consists of above-mentioned these components basically.
Can suitably under the situation that does not have any specific component, implement with the disclosed the present invention of the mode of enumerating at this, this component does not particularly point out or enumerates at this, and any compound can contain or not contain any at this substituting group of not mentioning especially.
At this reference element periodictable, this table is meant the table by Sargent-Welch Scientific Company layout, and class-mark is no.S-18806.
Speech " is substantially free of pigment and/or filler " and is meant pigment and/or the filler that composition does not contain or only contain trace fully, be generally zero or account for total composition heavy below 3%, preferably be less than 2%, more preferably less than 1%.
Speech " pigment or the filler that contain obvious amount " is meant that composition contains pigment and/or the filler more than trace, is at least 3% of composition gross weight usually.
In composition of the present invention, all compositions can or mix by the blending simultaneously of any suitable device.
Perhaps, the preparation method of the present composition can pass through any one component: two component blends of all the other of Resins, epoxy, carbonyl bearing polymer or stablizer and premix.
In addition, the present composition also can be by the preparation of such method, the pre-reaction product blend that is about to Resins, epoxy and carbonyl bearing polymer and stablizer and prepare.
Blend can be finished by any suitable device, for example driedly mixes, melt extrudes, two rollers are mixing or other melting mixing devices, perhaps their combination.
When composition by melt extruding when preparation, temperature should be controlled at the temperature that does not react between the carboxyl of the epoxy group(ing) of Resins, epoxy and carbonyl bearing polymer.The temperature that melt extrudes blend is preferably from 30 ℃ to 120 ℃, more preferably from 40 ℃ to 100 ℃, most preferably from 50 ℃ to 70 ℃.
In any above-mentioned blend method, the time that blend is carried out makes the gained blend even basically for being enough to.Basically evenly be meant dispersion equably in small, broken bits, not even as big as appreciable particle.
The preferred method that will contain the reactor product of carbonyl bearing polymer, carbonyl bearing polymer of carboxyl polymer or ionomer form and stablizer blend is that carbonyl bearing polymer and the Resins, epoxy with carbonyl bearing polymer or ionomer form carries out stepwise Co-mixturing, to form the Resins, epoxy with the carbonyl bearing polymer modification.The advantage of blend is to contain the distribution ratio of carbonyl polymerization thing in Resins, epoxy directly to be blended in the powder coating prescription it more even like this.In addition, the blend of the carbonyl bearing polymer of Resins, epoxy and carbonyl bearing polymer or ionomer form, preferably carry out in such condition, promptly can not cause the reaction between epoxy group(ing) and acidic group, the preferred temperature of this condition is between from 30 ℃ to 120 ℃, more preferably from 40 ℃ to 100 ℃, most preferably from 50 ℃ to 70 ℃.
In all compositions of the present invention, preferably use the carbonyl bearing polymer of ionomer form, this can be by finishing carbonyl bearing polymer and stabilizer compounds pre-reaction.
In preparation curable compositions and powder paint compositions, all components can add respectively, blend or melt extrude or other mixing or blend then, or any combination of mixing and blend.But, the pre-blend of preparation a kind of Resins, epoxy, carbonyl bearing polymer and stablizer earlier before all the other component blend of composition preferably, simultaneously carbonyl bearing polymer and stablizer with epoxy blend before by pre-blend or pre-reaction.
In improved composition epoxy resin of the present invention and curable compositions, stablizer, component (C) are to be enough to provide the use of following ratio, be metal equivalent and the ratio of carboxyl equivalent was at least 0.04: 1, preferably from 0.08: 1 to 6: 1, more preferably from 0.15: 1 to 1: 1.
Be suitable for doing in the composition of epoxy curing agent of the present invention, stablizer, component (3) are to be enough to the providing amount of following ratio to use, to be metal equivalent with the ratio of carboxyl equivalent be at least is preferably from 0.08: 1 to 6: 1 at 0.04: 1, more preferably from 0.15: 1 to 1: 1.
In the coating composition that contains obvious filler and/or pigment of the present invention, stablizer, component (C) are to be enough to the providing amount of following ratio to use, be metal equivalent and the ratio of carboxyl equivalent was at least 0.04: 1, be preferably from 0.08: 1 to 6: 1, more preferably from 0.15: 1 to 1: 1.
In the coating composition of essentially no filler of the present invention and/or pigment, stablizer, component (C) are to be enough to the providing amount of following ratio to use, be metal equivalent and the ratio of carboxyl equivalent was at least 0.5: 1, be preferably from 0.6: 1 to 6: 1, more preferably from 0.7: 1 to 1: 1.
In curable compositions of the present invention, the consumption of epoxy resin ingredient (A) is 66 to 99, is preferably from 80 to 96, and more preferably from 80 to 92% weight are with total restatement of epoxy tree (A) and carbonyl bearing polymer (B).
In curable compositions of the present invention, the consumption of carbonyl bearing polymer (B) is the total restatement from 1 to 33 with Resins, epoxy (A) and carbonyl bearing polymer (B), preferably from 4 to 20, and 8 to 20% weight more preferably.
In curable compositions of the present invention, the consumption of other solidifying agent, component (D) depends on used concrete solidifying agent, usually the consumption of other solidifying agent is from 0.8: 1 to 3: 1 for the ratio of the equivalent that can make this solidifying agent, component (D), the polymkeric substance that adds the carboxy-containing acid group or its ionomer, B component and the epoxy equivalent (weight) in the component (A), preferably from 0.9: 1 to 25: 1, more preferably from 1: 1 to 2: 1.
In curing agent composition of the present invention, carbonyl bearing polymer, the consumption from 1 to 99 of component (1), preferably from 3 to 96, more preferably from 25 to 90% weights are with total restatement of component (1) and (2).
In curing agent composition of the present invention, other solidifying agent or different solidifying agent, the consumption of component (2) counts from 99 to 1 with the gross weight of component (1) and (2), and is excellent from 97 to 4, more preferably from 75 to 10% weight.
In curing agent composition of the present invention, the consumption of promotor or catalyst component (if wish using these promotor or catalyzer) counts from 0.01 to 2 with the gross weight of all solidifying agent, and preferably from 0.1 to 1.5, more preferably from 0.2 to 0.8% weight.
Curing agent composition of the present invention can or melt extrude all components by simple blend and prepare.
Curable compositions can be by carrying out blend to its all components, mixing, melt extrude or their combination prepares.
The preparation of curing agent composition normally from 20 ℃ to 200 ℃ preferably from 50 ℃ to 150 ℃, more preferably carry out from 70 ℃ to 130 ℃ temperature, time should be enough to the time of production homogenizing product, be generally in 15 seconds to 2 hours time range, how together depend on these component blend.If use and extrude the preparation composition, then be fit to use short period of time from 15 seconds to 2 minutes.If use batch reactor or blender, then to use the long period, for example prepared composition until 2 hours from 5 minutes.
With the epoxy resin ingredient blend before or after the blend, must from the reaction between carbonyl bearing polymer and stabiliser composition, remove by product.But, if desired, can easily remove by product by composition being vacuumized also, and heating if desired, when vacuumizing, composition can make it be in the temperature of not damaging composition, be generally from room temperature or envrionment temperature to being no more than 120 ℃, preferably be no more than 100 ℃, more preferably no more than 70 ℃.Pressure can from 0 to 760, and preferably from 0 to 200, more preferably from 0 to 60mmHg post (definitely).
Resins, epoxy
Can comprise for example any Resins, epoxy that in its main chain, contains at least one aromatic ring in this suitable epoxy as component (A).
Specially suitable Resins, epoxy comprises the glycidyl ether as following various phenol: dihydric phenol, bis-phenol, phenol-or substituted phenol-aldehyde novolac resin, dihydric phenol or bis-phenol and per molecule affixture, phenol or the substituted phenol-unsaturated hydrocarbons resin of the alkylene oxide of 2 to 4 C atoms is arranged, or any two or more arbitrary combination of these compounds; Wherein said Resins, epoxy per molecule contains on average more than a glycidyl ether group.These compounds also can contain substituting group for example aliphatic saturated hydrocarbon, unsaturated aliphatic hydrocarbon, halogen (comprising chlorine, bromine, fluorine, iodine), nitro or nitrile.Equally, also available these halogens of hydrocarbon substituent (comprising fluorine, chlorine, bromine, iodine), nitro, nitrile replace.In addition, these compounds can be expressly without any one or more these substituent, equally, these replace hydrocarbon also can be expressly without any one or more these substituent, in addition, these compounds and replacement hydrocarbon can contain the substituting group of not mentioning especially at this, and these compounds and replacement hydrocarbon also can not be contained in the substituting group that this does not mention especially equally.
Preferred Resins, epoxy comprises the glycidyl ether as following various phenol: Resorcinol, pyrocatechol, Resorcinol, dihydroxyphenyl propane (4,4 '-different inferior diphenol), Bisphenol F (2,2 '-the dimethylene diphenol), bis-phenol K(4,4 '-the dihydroxyl diphenylketone), the cresols-Gao oligopolymer resin of the phenol-Gao oligopolymer resin of bisphenol S (4,4 '-alkylsulfonyl diphenol), fluorenes, phenol-formaldehyde phenolic resin varnish, cresols-formaldehyde phenolic resin varnish, phenol-Dicyclopentadiene (DCPD) resin, Dicyclopentadiene (DCPD), cresols-Dicyclopentadiene (DCPD) resin, Dicyclopentadiene (DCPD); The affixture of any combination of Resorcinol, pyrocatechol, Resorcinol, dihydroxyphenyl propane, Bisphenol F, bis-phenol K, bisphenol S or fluorenes and ethylene oxide, propylene oxide or oxybutylene or these alkylene oxides; Or any two kinds or the multiple combination of these glycidyl ethers.In addition, in any above-mentioned glycidyl ether each aromatic ring to contain from 1 to 2 halogen atom (preferably bromine) also be suitable.
Resins, epoxy of the present invention preferably has from 200 to 2000, and more preferably from 500 to 955, from 575 to 820 equivalent weight most preferably.It is basic calculation that equivalent weight does not have substituting group with the aromatic ring of Resins, epoxy, even they in fact contain substituting group.
Carboxy-containing acid group's polymkeric substance
Suitable polymers is by one or more ethylenically unsaturated monomers preparations, at least a hydroxy-acid group that contains in these monomers, this polymkeric substance can comprise that for example one or more have the alpha-olefin of from 2 to 10 C atoms and those multipolymers of one or more alkene unsaturated carboxylic acids or binary alkene unsaturated carboxylic acid half ester at this as component (B) or (1).
Specially suitable alpha-olefin comprises for example any composition of ethene, propylene, butylene, amylene, hexene, heptene, octene, nonene, decene or any two or more alpha-olefins.Ethene is preferred.
Specially suitable alkene unsaturated carboxylic acid comprises for example vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid.Preferably vinylformic acid, methacrylic acid, vinylformic acid is most preferred.
Specially suitable half ester comprises the C of toxilic acid, fumaric acid or methylene-succinic acid
1To C
10, preferred C
1To C
6, more preferably C
1To C
4The hydrocarbon half ester.These sour methyl, ethyl, propyl group, butyl, amyl group and hexyl half ester are more suitably.
Stabilizer component
Comprise for example organic carboxylate, zinc carbonate, zinc oxide, yellow soda ash, the salt of wormwood of periodic table of elements I A, II A, II B, III A, VI B or VIII family metal in this spendable suitable stabilizers; Or any combination of any of these stablizer.
Specially suitable stablizer comprises aliphatic or alicyclic or its aromatics organic carboxylate of the saturated or insatiable hunger of zinc oxide, yellow soda ash, zinc carbonate, salt of wormwood or sodium, lithium, potassium, zinc, calcium, magnesium, nickel, aluminium or chromium, this acid is that per molecule has from 1 to 30, preferably from 1 to 18, more preferably any two or more the combination of from 1 to 2 C atom or these compounds.Preferred this carboxylate salt comprises for example any two kinds or multiple any combination of zinc carbonate, zinc acetate, zinc propionate, Zinic stearas, sodium acetate, calcium propionate or these compounds.
Other solidifying agent
In curing agent composition or curable compositions or powder paint compositions, except carboxy-containing acid group's polymkeric substance or its ionomer, comprise two or more arbitrary combination of the binary of compound, aliphatic series, cyclic aliphatic or the aromatics of phenolic hydroxyl group group outside for example guanidine, biguanides, fat amine, arylamine, per molecule are on average more than one or polycarboxylic acid or acid anhydrides or these solidifying agent at the suitable solidifying agent of this available.
Comprise that at this solidifying agent that is especially suitable for use as component (D) or (2) for example cyanamide, neighbour-toluene biguanides, acid functional polyester, per molecule contain more than the compound of a phenolic group group or arbitrary combination of any two or more these solidifying agent, preferred solidifying agent is a Dyhard RU 100.
The definite consumption of solidifying agent depends on used concrete solidifying agent, usually the consumption of solidifying agent for the ratio that can make this solidifying agent and add carboxy-containing acid group's polymkeric substance or its ionomeric equivalent and epoxy equivalent (weight) for from 0.8: 1 to 3: 1, excellent in 0.9: 1 to 2.5: 1, more preferably from 1: 1 to 2: 1.
Promotor or catalyzer
Be used for promoting that the suitable promotor reacted between curing agent component and Resins, epoxy or catalyzer for example comprise primary, any two or more combination of the second month in a season or uncle's aliphatic series or cyclic aliphatic or aromatic amine, Lewis acid, Lewis base or these promotor or catalyzer.
Specially suitable promotor or catalyzer comprise imidazoles, the imidazoles of for example imidazoles, replacement and contain affixture, the substituted imidazole of epoxy compounds (for example single, double or polyglycidyl ether) and contain the affixture of epoxy compounds (for example single, double or polyglycidyl ether) or any two or more arbitrary combination of these promotor or catalyzer.Preferred promotor or catalyzer are two or more arbitrary combinations of the affixture of glyoxal ethyline, glyoxal ethyline and bisphenol A diglycidyl ether or these promotor or catalyzer.
The consumption of promotor depends on used concrete promotor and solidifying agent.Generally, the consumption of promotor counts from 0.01 to 2 with the gross weight of all solidifying agent, stabiliser composition and promotor or catalyzer, preferably from 0.1 to 1.5, more preferably from 0.2 to 0.8% weight.
Filler
The suitable filler that can be used for this comprises for example mineral filler, for example inorganic oxide, carbonate, vitriol or the silicate of periodic table of elements I A, II A, III A, II B, VI B or VIII family metal, or any two or more arbitrary combination of these fillers.Preferred filler is any two or more any combination of titanium oxide, lime carbonate, barium sulfate, Magnesium Silicate q-agent, strontium silicate or these fillers.
Pigment
Comprise for example any any two or more arbitrary combination that the inorganic or pigment dyestuff of required color or these pigment can be provided to composition in this available suitable pigments.
Flow ability modifying agent or flow control agent
Comprise for example acrylate copolymer at this available proper flow properties-correcting agent or flow control agent, (gathering) siloxanes, fluorocarbon, or any two or more arbitrary combination of these flow ability modifying agents or flow control agent.Preferred modifiers or flow control agent are acrylate copolymers.
Levelling agent
Comprise for example bitter almond oil camphor at the suitable levelling agent of this available.
All use with function at this used filler arbitrarily, pigment, flow ability modifying agent or flow control agent, levelling agent, that is: this tittle can make these special additives give coating required performance.This tittle will change with concrete Resins, epoxy, solidifying agent and additive therefor.
The consumption of filler is generally from 0 to 60, and preferably from 0 to 50, more preferably from 2 to 35% weight are with total restatement of composition.
The consumption of pigment is generally the total restatement from 0 to 50 with composition, and preferably from 0 to 40, more preferably from 2 to 35% weight.
The consumption of flow ability modifying agent or flow control agent is generally the total restatement from 0 to 5 with composition, and preferably from 0 to 3, more preferably from 0 to 2% weight.
The consumption of levelling agent is the total restatement from 0 to 2 with composition, preferably from 0 to 1.5, and more preferably from 0 to 0.5% weight.
Following Example is used for illustrating the present invention, but can not be interpreted as limiting the scope of the invention by any way.
Flow ability modifying agent
Flow ability modifying agent A is by the commercially available Moderez of Synthron Chemicals
TMMFR.
Filler
BS-1 is with the commercially available barium sulfate of Sparwite W-10 by Mountain Minerals.
BS-2 is with the commercially available barium sulfate of Baytes # 1 by Pfizer.
Pigment
Pigment A is with the commercially available carbon black of Raven 2000 by Columbia Chemicals.
The comparative example A
1. with the preparation of the Resins, epoxy of 8.0% weight carbonyl bearing polymer modification:
In 100mm Baker-Perkins twin screw extruder, carbonyl bearing polymer A and Resins, epoxy A are prepared this modified epoxy with 0.087: 1 weight ratio by the forcing machine melting mixing in 90 ℃-110 ℃ temperature.Product is extruded into thin slice and is placed on the cooling zone, then crushing.
2. powder coating preparation
The powder coating prescription is by preparing 1 modified epoxy, 80g solidifying agent B and 26g flow ability modifying agent A melting mixing above the 2000g.By in plastics bag, each component being vibrated together the dried blend of these components of preparation, melting mixing in Buss Condux PLK 46 forcing machines, forcing machine has two sections, and the temperature of section 1 is that 70 ℃, sections 2 are 90 ℃, screw rod is 70 ℃, and rotating speed is 200rpm.Extrudate is pressed into thin slice with cooling roller, and air cooling is worn into smalls with Brinkmann ZM-1 shredder, and crosses 150 order brass sieves (105 micropore).Part powder coated in two days after melting mixing.The part powder takes the aging coated after 43 days of normal temperature.Be sprayed onto on the cold-rolled steel sheet of grinding with 60KV with Gema type 710 electrostatic guns.The steel plate of powder coated is in 180 ℃ of bakings 15 minutes, air cooling.
Example 1
The powder coating prescription is by modified epoxy, 80g solidifying agent B, 26g flow ability modifying agent A and 80g CaPr with 2000g comparative example A-1
2Stablizer melting mixing and preparing, said composition is with mode identical with comparative example A-2 and identical time preparation and test.
Example 2
The powder coating prescription is by modified epoxy, 80g solidifying agent B, 26g flow ability modifying agent A and 240g CaPr with 2000g comparative example A-1
2Stablizer melting mixing and preparing, said composition is with mode identical with comparative example A-2 and identical time preparation and test.
Comparative Examples B
1. with the preparation of the Resins, epoxy of 20% weight carbonyl bearing polymer modification:
Contain 2000g carbonyl bearing polymer A and 8000g Resins, epoxy B prepares modified epoxy by fusion.By in plastics bag, these components being vibrated together the dried blend of these components of preparation, melting mixing in Buss Condux PLK46 forcing machine, forcing machine has two sections, and section 1 is that 70 ℃, sections 2 are that 80 ℃, screw rod are 70 ℃, rotating speed 200rpm.The modification extrudate is pressed into thin slice, air cooling, crushing with cooling roller.
2. the preparation of powder coating
The powder coating prescription is by preparing 1 other Resins, epoxy B, 48g solidifying agent A and the 10.06g flow ability modifying agent A melting mixing of modified epoxy, 600g above the 600g.By in plastics bag, each component being vibrated together the dried blend of these components of preparation, melting mixing in Buss Condux PLK46 forcing machine, forcing machine has two sections, and section 1 is that 70 ℃, sections 2 are that 90 ℃, screw rod are 70 ℃, and rotating speed is 200rpm.Extrudate is pressed into thin slice, air cooling, wears into smalls with Brinkmann ZM-1 shredder with cooling roller, and mistake 150 order brass sieves (105 micropore), part powder coated in two days after melting mixing, another part powder is at 36 ℃ of coateds after aging 23 hours.This powder uses the electrostatic spraying of Gema rifle to grinding on the cold-reduced sheet.The steel plate of powder coated is 180 ℃ of bakings 15 minutes and in air cooling.
Comparative Examples C
The powder coating prescription is by Resins, epoxy B, 48g solidifying agent A and 10.06g flow ability modifying agent A and the 12g CaPr that modified epoxy, the 600g of 600g Comparative Examples B-1 is other
2Stablizer melting mixing and preparing.Said composition is with mode identical with Comparative Examples B-2 and identical time preparation and test.
Example 3
The powder coating prescription is by Resins, epoxy B, 48g solidifying agent A and 10.06g flow ability modifying agent A and the 24g CaPr that modified epoxy, the 600g of 600g Comparative Examples B-1 is other
2Stablizer melting mixing and preparing.Said composition is with mode identical with Comparative Examples B-2 and identical time preparation and test.
Example 4
The powder coating prescription is by Resins, epoxy B, 48g solidifying agent A and 10.06g flow ability modifying agent A and the 48g CaPr that modified epoxy, the 600g of 600g Comparative Examples B-1 is other
2Stablizer melting mixing and preparing.Said composition is with mode identical with Comparative Examples B-2 and identical time preparation and test.
Comparative Examples D
1. with the preparation of 20% weight carbonyl bearing polymer modified epoxy:
B-1 is identical with Comparative Examples.
2. the preparation of powder coating
The powder coating prescription is by with 1 modified epoxy above the 600g, Resins, epoxy B, 48g solidifying agent A, 245g BS-2 filler, 22.97g pigment A and the 15.31g flow ability modifying agent A melting mixing that 600g is other and preparing.By in plastics bag, these components being vibrated together the dried blend of these components of preparation, melting mixing in Buss Condux PLK46 forcing machine, forcing machine has two sections, and section 1 is that 70 ℃, sections 2 are that 90 ℃, screw rod are 70 ℃, rotating speed 200rpm.Forcing machine is pressed into thin slice with cooling roller, and air cooling is clayed into power with Brinkmam ZM-1 shredder, and crosses 150 order brass sieves.Partly powder melting mixing one day after in coated, another partly 40 ℃ wore out 20 hours after coated.Powder uses the electrostatic spraying of Gema rifle to grinding on the cold-rolled steel sheet.The steel plate of powder coated is in 180 ℃ of bakings 15 minutes and air cooling.
Example 5
Powder coated prescription is by the Resins, epoxy B that modified epoxy, the 600g of 600g Comparative Examples D-1 is other, 48g solidifying agent A, 247g BS-2 filler, 23.19g pigment A and 15.46g flow ability modifying agent A and 12g CaPr
2Numeral agent melting mixing and preparing, said composition is with mode identical with Comparative Examples D-2 and identical time preparation and test.
Example 6
Powder coated prescription is by the Resins, epoxy B that modified epoxy, the 600g of 600g Comparative Examples D-1 is other, 48g solidifying agent A, 250g BS-2 filler, 23.41g pigment A and 15.61g flow ability modifying agent A and 24g CaPr
2Stablizer melting mixing and preparing, said composition is with mode identical with Comparative Examples D-2 and identical time preparation and test.
Example 7
Powder coated prescription is by the Resins, epoxy B that modified epoxy, the 600g of 600g Comparative Examples D-1 is other, 48g solidifying agent A, 254g BS-2 filler, 23.85g pigment A and 15.90g flow ability modifying agent A and 48g CaPr
2Stablizer melting mixing and preparing, said composition is with mode identical with Comparative Examples D-2 and identical time preparation and test.
Comparative Examples E
1. with the preparation of the Resins, epoxy of the carbonyl bearing polymer modification of 15% weight:
Prepare modified epoxy by melting mixing 1800g carbonyl bearing polymer A and 10200g Resins, epoxy B.By in plastics bag, each component being vibrated together the dried blend of these components of preparation, melting mixing in Buss Condux PLK46 forcing machine, forcing machine has two sections, and section 1 is that 70 ℃, sections 2 are that 90 ℃, screw rod are 70 ℃, rotating speed 200rpm.This modified epoxy extrudate is pressed into thin slice with cooling roller, air cooling and crushing.
2. the preparation of powder coating
The powder coating prescription is by with 1 the other Resins, epoxy B of modified epoxy, 600g above the 1200g, 72g solidifying agent A and 18.9g flow ability modifying agent A melting mixing and prepare.By in plastics bag, each component being vibrated together the dried blend of these components of preparation, melting mixing in Buss Condux PLK46 forcing machine, forcing machine has two sections, and section 1 is that 70 ℃, sections 2 are that 90 ℃, screw rod are 70 ℃, rotating speed 200rpm.Extrudate is pressed into thin slice with cooling roller, and air cooling is clayed into power with Brinkmam ZM-1 shredder, and cross the yellow steel of 150 orders and sieve, powder coated in two days after melting mixing partly, partly powder is at 40 ℃ of coateds after aging 24 hours, and partly powder is at normal temperature coated after aging 27 days.This powder uses the electrostatic spraying of Gema rifle to the cold-rolled steel sheet that grinds.Powder coated steel plate is in 180 ℃ of bakings 15 minutes and air cooling.
Example 8
The powder coating prescription is by Resins, epoxy B, 72g solidifying agent A, 19.2g flow ability modifying agent A and the 31.2g CaPr that modified epoxy, the 600g of 1200g Comparative Examples E-1 is other
2Stablizer melting mixing and preparing.Said composition is with mode identical with Comparative Examples E-2 and identical time preparation and test.
Example 9
The powder coating prescription is by Resins, epoxy B, 72g solidifying agent A, 19.3g flow ability modifying agent A and the 37.2g ZnAc that modified epoxy, the 600g of 1200g Comparative Examples E-1 is other
2Stablizer melting mixing and preparing.Said composition is with mode identical with Comparative Examples E-2 and identical time preparation and test.
Example 10
The powder coating prescription is by Resins, epoxy B, 72g solidifying agent A, 20.0g flow ability modifying agent A and the 105.6g ZnSt that modified epoxy, the 600g of 1200g Comparative Examples E-1 is other
2Stablizer melting mixing and preparing.Said composition is with mode identical with Comparative Examples E-2 and identical time preparation and test.
Comparative Examples F
1. with the preparation of the Resins, epoxy of 15% weight carbonyl bearing polymer modification:
Prepare modified epoxy by melting mixing 900g carbonyl bearing polymer A and 5100g Resins, epoxy B.By in plastics bag, each component being vibrated together the dried blend of these components of preparation, melting mixing in Buss Condux PLK46 forcing machine, forcing machine has two sections, and section 1 is that 70 ℃, sections 2 are that 80 ℃, screw rod are 70 ℃, rotating speed 212rpm.The modified epoxy extrudate is pressed into thin slice with cooling roller, air cooling and crushing.
2. the preparation of powder coating
The powder coating prescription is by with 1 modified epoxy above the 1500g, 60g solidifying agent A and 300g BS-1 filler, 28.6g pigment A and 19.1 flow modifier A melting mixing and prepare.By in plastics bag, each component being vibrated together the dried blend of these components of preparation, melting mixing in Buss Condux PLK46 forcing machine, forcing machine has two sections, and section 1 is that 70 ℃, sections 2 are that 80 ℃, screw rod are 70 ℃, rotating speed 212rpm.Extrudate is pressed into thin slice with cooling roller, and air cooling is clayed into power with Brinkmam ZM-1 shredder, and crosses 150 order brass sieves.Coated in the part powder melts is mixed one day after, the part powder is at 40 ℃ of coateds after aging 24 hours.Another part powder is coated after normal temperature wore out 33 days, and this powder sprays on the cold-rolled steel sheet of grinding with Wagner G100 EPB electrostatic gun.The steel plate of powder coated is in 180 ℃ of bakings 15 minutes and air cooling.
Example 11
A. the preparation of the pre-reaction product of carbonyl bearing polymer and metal-salt:
The pre-reaction product (ionomer) of carbonyl bearing polymer A 11.7g/ minute CaPr of melting mixing
2Carbonyl bearing polymer A was at Werner and Pfleiderer(WP in stablizer and 270g/ minute) in the 30mm twin screw extruder and prepare.Barrel zone temperature: section 1 is 52 ℃, and a section 2-5 is 113 ℃-121 ℃, and this product is extruded by 3 strands of moulds, and water cooling is cut to the particle of 1/4 inch (6.35mm).
B. use the preparation of Resins, epoxy of the carbonyl bearing polymer modification of 15% weight:
Calcium ionomer and 5100g Resins, epoxy B by the carbonyl bearing polymer A for preparing among the A above the melting mixing 900g prepare the Resins, epoxy of modification, and said composition is according to the method preparation identical with the modified resin of Comparative Examples F-1.
C. the preparation of powder coating
The powder coating prescription prepares by modified epoxy, 60g solidifying agent A, 300g BS-1 filler, 28.6g pigment A and the 19.1g flow ability modifying agent A melting mixing with B above the 1500g.Said composition is with mode identical with Comparative Examples F-2 and identical time preparation and test.
Example 12
A. the preparation of the pre-reaction product of carbonyl bearing polymer and metal-salt:
The pre-reaction product (ionomer) of carbonyl bearing polymer A is at Werner and Pfleiderer(WP) prepare by molten mixture A in the 30mm twin screw extruder.Barrel zone temperature: section 1 is 52 ℃, and a section 2-5 is 113 ℃-121 ℃, and this product is extruded by 3 strands of moulds, and the particle of 1/4 inch (6.35mm) is cut in water cooling.
B. use the preparation of Resins, epoxy of the carbonyl bearing polymer modification of 15% weight:
Zinc ionomer and 5100g Resins, epoxy B by the carbonyl bearing polymer A for preparing among the A above the melting mixing 900g prepare the Resins, epoxy of modification, and said composition is with the method preparation identical with the modified resin of Comparative Examples F-1.
C. the preparation of powder coating
The powder coating prescription prepares by modified epoxy, 60g solidifying agent A, 300g BS-1 filler, 28.6g pigment A and the 19.1g flow ability modifying agent A melting mixing with B above the 1500g.Said composition is with mode identical with Comparative Examples F-2 and identical time preparation and test.
Comparative Examples G
1. with the preparation of the Resins, epoxy that contains the modification of carbonyl polymerization thing of 15% weight:
Prepare modified epoxy by melting mixing 900g carbonyl bearing polymer A and 3400g Resins, epoxy B.By in plastics bag, each component being vibrated together the dried blend of these components of preparation, melting mixing in Buss Condux PLK46 forcing machine, forcing machine has two sections, and section 1 is that 70 ℃, sections 2 are that 80 ℃, screw rod are 70 ℃, rotating speed 200rpm.This modified epoxy extrudate is pressed into thin slice with cooling roller, air cooling and crushing.
2. the preparation of powder coating
The powder coating prescription is by with 1 modified epoxy above the 1500g, 60g solidifying agent A, 300g BS-1 filler, 28.6g pigment A and 19.1 flow ability modifying agent A melting mixing and prepare.By in plastics bag, each component being vibrated together the dried blend of these components of preparation, melting mixing in Buss Condux PLK46 forcing machine, forcing machine has two sections, and section 1 is that 70 ℃, sections 2 are that 80 ℃, screw rod are 70 ℃, rotating speed 200rpm.This extrudate is pressed into thin slice with cooling roller, and air cooling is clayed into power with Brinkmam ZM-1 shredder, and crosses 150 order brass sieves.The part powder melts is coated in mixing one day after, and the part powder is at 40 ℃ of coateds after aging 24 hours, powder with the electrostatic spraying of Wagner rifle to the cold-rolled steel sheet of grinding.The steel plate of powder coated is in 180 ℃ of bakings 15 minutes and air cooling.
Example 13
A. the preparation of the pre-reaction product of carbonyl bearing polymer and metal-salt:
The pre-reaction product (ionomer) of carbonyl bearing polymer A is the ZnAc that passed through in WP 30mm twin screw extruder melting mixing 8.8g/ minute
2Stablizer and 335g/ minute carbonyl bearing polymer A and prepare.Barrel zone temperature: section 1 is 53 ℃, and a section 2-5 is 109 ℃-117 ℃, and product is extruded by 3 strands of moulds, and water cooling is cut to the particle of 1/4 inch (6.35mm).
B. use the preparation of Resins, epoxy of the carbonyl bearing polymer modification of 15% weight:
Zinc ionomer and 3400g Resins, epoxy B by the carbonyl bearing polymer A for preparing among the A above the melting mixing 600g prepare the Resins, epoxy of modification, and said composition is according to the method preparation identical with the modified resin of Comparative Examples F-1.
C. the preparation of powder coating
The powder coating prescription prepares by modified epoxy, 60g solidifying agent A, 300g BS-1 filler, 28.6g pigment A and the 19.1g flow ability modifying agent A melting mixing with B above the 1500g.Said composition is with mode identical with Comparative Examples F-2 and identical time preparation and test.
Example 14
A. the preparation of the pre-reaction product of carbonyl bearing polymer and metal-salt:
The pre-reaction product (ionomer) of carbonyl bearing polymer A is the ZnAc that passed through in WP 30mm twin screw extruder melting mixing 17.1g/ minute
2Stablizer and 335g/ minute carbonyl bearing polymer A and prepare.Barrel zone temperature: section 1 is 51 ℃, and a section 2-5 is 105 ℃-116 ℃, and product is extruded by 3 strands of moulds, and water cooling is cut to the particle of 1/4 inch (6.35mm).
B. use the preparation of Resins, epoxy of the carbonyl bearing polymer modification of 15% weight:
Zinc ionomer and 3400g Resins, epoxy B by the carbonyl bearing polymer A for preparing among the A above the melting mixing 600g prepare the Resins, epoxy of modification, and said composition is according to the method preparation identical with the modified resin of Comparative Examples G-1.
C. the preparation of powder coating
The powder coating prescription prepares by modified epoxy, 60g solidifying agent A, 300g BS-1 filler, 28.6g pigment A and the 19.1g flow ability modifying agent A melting mixing with B above the 1500g.Said composition is with mode identical with Comparative Examples F-2 and identical time preparation and test.
Example 15
A. the preparation of powder coating
The powder coating prescription is by modified epoxy, 60g solidifying agent A, 300g BS-1 filler, 28.6g pigment A and 19.1g flow ability modifying agent A and 11.25g ZnAc with 1500g Comparative Examples G-1
2Stablizer melting mixing and preparing.Said composition is with mode identical with Comparative Examples G-2 and identical time preparation and test.
Comparative Examples H
1. with the preparation of the Resins, epoxy that contains the modification of carbonyl polymerization thing of 15% weight:
The carbonyl bearing polymer A and the Resins, epoxy B that extrude the melting mixing weight ratio and be 0.85: 1 in 100ml Baker-Perkins twin screw extruder under 90 ℃-110 ℃ temperature prepare modified epoxy.This product is extruded thin slice and is placed on the cooling zone, then crushing.
2. the preparation of powder coating
The powder coating prescription is by with 1 modified epoxy above the 1500g, 60g solidifying agent A, 300g BS-1 filler, 28.6g pigment A and 19.1 flow ability modifying agent A melting mixing and prepare.By in plastics bag, each component being vibrated together the dried blend of these components of preparation, melting mixing in Buss Condux PLK46 forcing machine, forcing machine has two sections, and section 1 is that 70 ℃, sections 2 are that 80 ℃, screw rod are 70 ℃, rotating speed 200rpm.This extrudate is pressed into thin slice with cooling roller, and air cooling is clayed into power with Brinkmam ZM-1 shredder, and crosses 150 order brass sieves.The part powder melts is coated in mixing one day after, the part powder 40 ℃ wore out 24 hours after coated.This powder uses the electrostatic spraying of Wagner rifle to the cold-rolled steel sheet that grinds.The steel plate of powder coated is in 180 ℃ of bakings 15 minutes and air cooling.
Example 16
A. the pre-reaction product for preparing carbonyl bearing polymer and metal-salt:
The pre-reaction product (ionomer) of carbonyl bearing polymer A is that the carbonyl bearing polymer A by melting mixing 22.5g/ minute NaAc stablizer and 355g/ minute prepares in WP 30mm twin screw extruder.Barrel zone temperature: section 1 is that 50 ℃, section 2-5 are 104 ℃-107 ℃.This product has passed through the demoulding to be extruded, and water cooling also is cut into the particle of 1/4 inch (6.35mm).
B. use the preparation of Resins, epoxy of the carbonyl bearing polymer modification of 15% weight:
Zinc ionomer and 3400g Resins, epoxy B by melting mixing 600g carbonyl bearing polymer A prepare the Resins, epoxy of modification.Said composition is with the method preparation same with the modified resin of Comparative Examples G-1.
C. the preparation of powder coating
The powder coating prescription prepares by modified epoxy, 60g solidifying agent A, 300g BS-1 filler, 28.6g pigment A and the 19.1 flow ability modifying agent A melting mixing with B above the 1500g.Said composition is with mode identical with Comparative Examples H-2 and identical time preparation and test.
Example 17
A. the preparation of the pre-reaction product of carbonyl bearing polymer and metal-salt:
The pre-reaction product (ionomer) of carbonyl bearing polymer A is the ZnAc that passed through in WP 30mm twin screw extruder melting mixing 47.3g/ minute
2Stablizer and 335g/ minute carbonyl bearing polymer A and prepare.Barrel zone temperature: section 1 is 48 ℃, and section 2-5 is 105 ℃-113 ℃.This product is extruded by 3 strands of moulds, and water cooling is cut to the particle of 1/4 inch (6.35mm).
B. use the preparation of Resins, epoxy of the carbonyl bearing polymer modification of 15% weight:
Zinc ionomer and 3400g Resins, epoxy B by the carbonyl bearing polymer A for preparing among the A above the melting mixing 600g prepare the Resins, epoxy of modification, and said composition is according to the method preparation identical with the modified resin of Comparative Examples G-1.
C. the preparation of powder coating
The powder coating prescription prepares by modified epoxy, 60g solidifying agent A, 300g BS-1 filler, 28.6g pigment A and the 19.1g flow ability modifying agent A melting mixing with B above the 1500g.Said composition is with mode identical with Comparative Examples H-2 and identical time preparation and test.
Example 18
A. the preparation of powder coating
The powder coating prescription prepares by modified epoxy, 60g solidifying agent A, 300g BS-1 filler, 28.6g pigment A and the 19.1g flow ability modifying agent A melting mixing with 1500g Comparative Examples G-1.Said composition is with mode identical with Comparative Examples H-2 and identical time preparation and test.
Example 19
A. the preparation of the pre-reaction product of carbonyl bearing polymer and metal-salt:
The pre-reaction product (ionomer) of carbonyl bearing polymer A is the ZnSt that passed through in WP 30mm twin screw extruder melting mixing 48.2g/ minute
2Stablizer and 335g/ minute carbonyl bearing polymer A and prepare.Barrel zone temperature: section 1 is 56 ℃, and section 2-5 is 128 ℃-139 ℃.This product is extruded by 3 strands of moulds, and water cooling is cut to the particle of 1/4 inch (6.35mm).
B. use the preparation of Resins, epoxy of the carbonyl bearing polymer modification of 15% weight:
Zinc ionomer and 3400g Resins, epoxy B by melting mixing 600g carbonyl bearing polymer A prepare the Resins, epoxy of modification, and said composition is according to the method preparation identical with the modified resin of Comparative Examples G-1.
C. the preparation of powder coating
The powder coating prescription prepares by modified epoxy, 60g solidifying agent A, 300g BS-1 filler, 28.6g pigment A and the 19.1g flow ability modifying agent A melting mixing with B above the 1500g.Said composition is with mode identical with Comparative Examples H-2 and identical time preparation and test.
Example 20
A. the pre-reaction product for preparing carbonyl bearing polymer and metal-salt:
The pre-reaction product (ionomer) of carbonyl bearing polymer A is that the weight ratio by the about 4000g of melting mixing is 0.0488: 1 ZnAc in WP 30mm twin screw extruder
2The dried blended mixture of the ion product (ionomer) of stablizer and carbonyl bearing polymer A and preparing.Barrel zone temperature: section 1 is 44 ℃, and section 2-5 is 103 ℃-111 ℃.Pressure is that the vacuum port of 20mm Hg absolute value is removed by-product acetic acid.Product is extruded by 3 strands of moulds, and water cooling is cut to the particle of 1/4 inch (6.35mm).
B. use the preparation of Resins, epoxy of the carbonyl bearing polymer modification of 15% weight:
Zinc ionomer and 2550g Resins, epoxy B by the carbonyl bearing polymer A for preparing among the A above the melting mixing 450g prepare the Resins, epoxy of modification, by in plastics bag, each component being vibrated together the dried blend of these components of preparation, melting mixing in Buss Condux PLK46 forcing machine, it is 20 ℃ that forcing machine has two section, sections 1, section 2 is 70 ℃, and screw speed is 200rpm.Forcing machine is pressed into thin slice with cooling roller, air cooling and crushing.
C. the preparation of powder coating
The powder coating prescription prepares by modified epoxy, 62.9g solidifying agent A, 315g BS-1 filler, 30g pigment A and the 20g flow ability modifying agent A melting mixing with B above the 1570g.By in plastics bag, each component being vibrated together the dried blend of these components of preparation, in melting mixing in Buss Condux PLX 46 forcing machines, it is 50 ℃ that forcing machine has two section, sections, 1 temperature, and section 2 is that 80 ℃, screw rod are 50 ℃, and rotating speed is 200rpm.Extrudate is pressed into thin slice, air cooling with cooling roller, clays into power with Brinkmam ZM-1 shredder, crosses 150 order brass sieves.Partly powder melting mixing one day after in coated, partly powder is at 40 ℃ of aging 24 hours coateds for another, on the cold steel plate that grinds, the steel plate of powder coated is in 180 ℃ of bakings also air cooling in 15 minutes with the electrostatic spraying of Wagner rifle for this powder.
Example 21
A. the preparation of the pre-reaction product of carbonyl bearing polymer and metal-salt:
The pre-reaction product (ionomer) of carbonyl bearing polymer A is the ZnCo that passed through in WP 30mm twin screw extruder melting mixing 120.6g/ minute
3Stablizer and 4324g carbonyl bearing polymer A and prepare.Barrel zone temperature: section 1 is 46 ℃, and section 2-5 is 105 ℃-111 ℃.Pressure is that the vacuum port of 20mm Hg absolute value is removed byproduct water.This product is extruded by 3 strands of moulds, and water cooling is cut to the particle of 1/4 inch (6.35mm).
B. use the preparation of Resins, epoxy of the carbonyl bearing polymer modification of 15% weight:
Zinc ionomer and 2550g Resins, epoxy B by the carbonyl bearing polymer A for preparing among the A above the melting mixing 450g prepare the Resins, epoxy of modification, and said composition is according to the method preparation identical with the modified resin of Comparative Examples 20-B.
C. the preparation of powder coating
The powder coating prescription prepares by modified epoxy, 62.9g solidifying agent A, 315g BS-1 filler, 30g pigment A and the 20g flow ability modifying agent A melting mixing with B above the 1570g.Said composition prepares in the mode identical with Comparative Examples 20-C.
Following table I has been made brief description to above these embodiment and Comparative Examples.Embodiment and the common ground parallel grouping of Comparative Examples by them.
The table I
The brief description of embodiment is by these routine concurrent groupings
* non-example of the present invention.
Table I (continuing)
The brief description of embodiment is by these routine concurrent groupings
* non-example of the present invention
Table I (continuing)
The brief description of embodiment is by these routine concurrent groupings
Table I (continuing)
The brief description of embodiment is by these routine concurrent groupings
* non-example of the present invention.
Below table II brief description the ionomeric processing condition of preparation carbonyl bearing polymer.
The table II
Fusion on Werner and Pfleiderer 30mm forcing machine
Be mixed with the ionomeric brief description table of carbonyl bearing polymer
1.CaPr
2: calcium propionate, ZnAc
2: zinc acetate; NaAc: sodium-acetate; ZnSt
2: Zinic stearas.
2. the equivalence ratio of metal ion and acidic group.
3. metal ion changes into the ionomeric percentage ratio of carbonyl bearing polymer.
4. of no use.The ionomer premix of metal-salt and carbonyl bearing polymer, the feed rate of indication is for mixture.
5. do not determine.
Annotate: spiro rod rate all is 400rpm to all examples, except example 19 is 477rpm.
Below table III brief description the preparation of modified epoxy.
The table III
The brief description table of preparation modified epoxy, fusion
Mixing is to carry out (unless other explanation is arranged) on forcing machine
The table III
The brief description table of preparation modified epoxy, fusion
Mixing is to carry out (unless other explanation is arranged) on forcing machine
* non-example of the present invention;
1. Resins, epoxy A;
2. carboxy-containing copolymer;
3. Resins, epoxy B;
4.CaPr
2=calcium propionate, ZnAc=zinc acetate, NaAc=sodium-acetate;
ZnSt
2=Zinic stearas; ZnCO
3=zinc carbonate.
Below table IV brief description the recipe ingredient of each Comparative Examples and embodiment.
Below table V brief description the compare relative variation of glossiness of coating and the new coating of powder of coat-thickness, coating gloss and aging powder.
The table V
The brief description table of coating performance
* non-example of the present invention.
Claims (20)
1, a kind of improved composition epoxy resin includes:
(A) at least a Resins, epoxy contains average per molecule more than an ortho position epoxy group(ing), and on its main chain at least an aromatic ring; With
(B) at least a polymkeric substance by one or more ethylenically unsaturated monomers preparations, at least a hydroxy-acid group that contains in these monomers;
It is characterized in that having added in the described composition
(C) at least a stabilizer compounds of stable quantity, it is:
(a) at least a periodic table of elements I A, II A, II B, III A, VI B or VIII family metal organic carboxylate;
(b) at least a following compound: zinc carbonate, zinc oxide, yellow soda ash or salt of wormwood;
(c) any (a) and combination (b).
2, a kind of curable compositions includes:
(A) at least a Resins, epoxy contains average per molecule more than an ortho position epoxy group(ing), and has an aromatic ring on its main chain at least;
(B) at least a polymkeric substance by one or more ethylenically unsaturated monomers preparations, at least a hydroxy-acid group that contains in these monomers; With
(D) be used at least a solidifying agent of the curing amount of component (A), it both had been different from component (B) and also had been different from component (B) and pre-reaction product (C);
It is characterized in that in described composition, adding
(C) at least a stabilizer compounds of stable quantity, it is:
(a) at least a periodic table of elements I A, II A, II B, III A, VI B or VIII family metal organic carboxylate;
(b) at least a following compound: zinc carbonate, zinc oxide, yellow soda ash or salt of wormwood; Or
(c) any (a) and combination (b).
3, a kind of powder paint compositions, its essentially no pigment and filler comprise:
(A) at least a Resins, epoxy contains average per molecule more than an ortho position epoxy group(ing), and has an aromatic ring on its main chain at least;
(B) at least a polymkeric substance by one or more ethylenically unsaturated monomers preparations, at least a hydroxy-acid group that contains in these monomers;
(D) be used at least a solidifying agent of the curing amount of component (A), it both had been different from component (B) and also had been different from component (B) and pre-reaction product (C);
(E) at least a or multiple interpolation component is selected from flow control agent, homogenizing auxiliary agent, promotor or catalyzer.
It is characterized in that in described composition, having added
(C) at least a stabilizer compounds of stable quantity, it is:
(a) at least a periodic table of elements I A, II A, II B, III A, VI B or VIII family metal organic carboxylate;
(b) at least a following compound: zinc carbonate, zinc oxide, yellow soda ash or salt of wormwood; Or
(c) any (a) and combination (b).
4, a kind of powder paint compositions, it contains the pigment of significant quantity or filler or both has, and comprises:
(A) at least a Resins, epoxy contains average per molecule more than an ortho position epoxy group(ing), and has an aromatic ring on its main chain at least;
(B) at least a polymkeric substance by one or more ethylenically unsaturated monomers preparations, at least a hydroxy-acid group that contains in these monomers;
(D) be used at least a solidifying agent of the curing amount of component (A), it both had been different from component (B) and also had been different from component (B) and pre-reaction product (C);
(E) at least a or multiple interpolation component comprises pigment, filler, flow control agent, homogenizing auxiliary agent, promotor or catalyzer.
It is characterized in that in described composition, having added
(C) at least a stabilizer compounds of stable quantity, it is:
(a) at least a periodic table of elements I A, II A, II B, III A, VI B or VIII family metal organic carboxylate;
(b) at least a following compound: zinc carbonate, zinc oxide, yellow soda ash or salt of wormwood; Or
(c) any (a) and combination (b).
5, claim 1,2,3 or 4 composition, wherein:
(a) composition branch (A) is the diglycidyl ether of following compound: dihydric phenol, bis-phenol, phenol-or replace phenol-formaldehyde resin or phenol-or phenol-unsaturated diene resin of replacing;
(b) component (B) is a kind of polymkeric substance, obtains by containing ethene and monomer mixture polymerization aliphatic, alicyclic or the aromatic carboxylic acid;
(c) component (C) is the have an appointment saturated or undersaturated aliphatic series of 1 to 30C atom of the per molecule of zinc oxide, yellow soda ash, zinc carbonate, salt of wormwood or sodium, lithium, potassium, zinc, calcium, magnesium, nickel, aluminium or chromium, the organic carboxylate of alicyclic or aromatics; Or any two or more combination of these compounds;
(d) component (D) is two or the multi-carboxy anhydride that guanidine, two guanidines, aliphatic amine, aromatic amine, per molecule contain on average compound more than a phenolic hydroxyl group, aliphatic series, alicyclic or aromatics, or two or more combinations of these solidifying agent;
(e) component (A) accounts for from about 66 to about 99% weight use with component (A) and total restatement (B);
(f) component (B) accounts for from about 1 to about 34% weight use with component (A) and total restatement (B);
(g) component (C) is used with such amount, and it is as follows that this amount is enough to provide the metal equivalent and the ratio of every carboxyl equivalent:
(ⅰ) in claim 1,2 or 4, be at least about 0.04: 1; Or
(ⅱ) in claim 3, be at least about 0.5: 1;
(h) component (D) is used with such amount, and this amount is enough to make this solidifying agent to add that component (B) or its ionomeric equivalent and the ratio of every epoxy equivalent (weight) satisfy from about 0.8: 1 to about 3: 1.
6, the composition of claim 5, wherein:
(a) component (A) is the diglycidylether of bis-phenol;
(b) component (B) is the polymkeric substance that is obtained by the monomer mixture polymerization that contains ethene and vinylformic acid or methacrylic acid;
(c) component (C) is zinc oxide, yellow soda ash, zinc carbonate, salt of wormwood, zinc acetate, zinc propionate, Zinic stearas, sodium acetate or calcium propionate;
(d) component (D) is dicyano diamines, neighbour-toluene biguanides, acid functional polyester, and per molecule contains more than the compound of a phenolic group group or any two or more combinations of these solidifying agent;
(e) component (A) is counted from the about 80 amount uses to about 96% weight with component (A) and gross weight (B);
(f) component (B) is counted from the about 4 amount uses to about 20% weight with component (A) and gross weight (B);
(g) component (C) is used with such amount, and this amount is enough to make the metal equivalent and the ratio of every carboxyl equivalent to satisfy:
(ⅰ) in claim 1,2 or 4, from about 0.08: 1 to about 6: 1; Or
(ⅱ) in claim 3 from about 0.6: 1 to about 6: 1;
(h) component (D) is used with such amount, and this amount makes this solidifying agent add that component (B) or its ionomeric equivalent and the ratio of every epoxy equivalent (weight) satisfy from about 0.9: 1 to about 2.5: 1.
7, according to the composition of claim 5, wherein:
(a) component (A) is the diglycidylether of dihydroxyphenyl propane, Bisphenol F or bis-phenol K;
(b) component (B) is by containing the polymkeric substance that ethene and acrylic acid monomer mixture polymerization obtain;
(c) component (C) is zinc carbonate, zinc acetate, zinc propionate, Zinic stearas, sodium acetate, calcium propionate or their any combination;
(d) component (D) is the promoted dicyano diamines of dicyano diamines or imidazoles;
(e) component (A) is to make up (A) and total restatement (B) from the about 80 amount uses to about 92% weight;
(f) component (B) is to use from about 8 to about 20% weight and amount with component (A) and total restatement (B);
(g) component (C) is to use with such amount, and this amount is enough to make the metal equivalent and the ratio of every carboxyl equivalent to satisfy:
(ⅰ) in claim 1,2 or 4, from about 0.15: 1 to about 1: 1; Or
(ⅱ) in claim 3, from about 0.7: 1 to about 1: 1;
(h) component (D) is to use with such amount, and this amount makes ratio that this solidifying agent adds component (B) or its ionomeric equivalent and every epoxy equivalent (weight) for from about 1: 1 to about 2: 1.
8, a kind of composition that is suitable for as epoxy curing agent comprises:
(1) at least a polymkeric substance, by one or more ethylenically unsaturated monomers preparations, at least one contains hydroxy-acid group in these monomers;
(2) at least aly be used for described curing agent for epoxy resin, this solidifying agent is different from component (1);
It is characterized in that in described curing agent composition, having added:
(3) stabilizer compounds of at least a stable quantity, they are:
(a) at least a periodic table of elements I A, II A, II B, III A, VI B or VIII family metal salt of organic carboxylic acid;
(b) at least a following compound: zinc carbonate, zinc oxide, yellow soda ash or salt of wormwood; Or
(c) any (a) and combination (b).
9, the composition of claim 8, wherein:
(a) component (1) is to exist from about 1 amount to about 99% weight with component (1) and (2) and total restatement;
(b) component (2) is to exist from about 99 amounts to about 1% weight with total restatement of component (1) and (2); With
(c) component (3) is to use with such amount, and this amount is enough to make the metal equivalent and the ratio of every carboxyl equivalent to satisfy at least about 0.04: 1.
10, the composition of claim 8, wherein:
(a) component (1) is to exist from about 3 amounts to about 96% weight with component (1) and (2) and total restatement;
(b) component (2) is to exist from about 97 amounts to about 4% weight with total restatement of component (1) and (2); With
(c) component (3) is to use with such amount, and this amount is enough to make the metal equivalent and the ratio of every carboxyl equivalent to satisfy at least about 0.08: 1 to about 6: 1.
11, the composition of claim 8, wherein:
(a) component (1) is to exist from about 25 amounts to about 90% weight with component (1) and (2) and total restatement; With
(b) component (2) is to exist from about 75 amounts to about 10% weight with total restatement of component (1) and (2); With
(c) component (3) is to use with such amount, and this amount is enough to make the metal equivalent and the ratio of every carboxyl equivalent to satisfy at least about 0.15: 1 to about 1: 1.
12, the composition of claim 11 has wherein used curing catalyst or catalyzer.
13, the product that obtains by the curable compositions that solidifies claim 3 or 4.
14, the product that obtains by the curable compositions that solidifies claim 5.
15, the product that obtains by the curable compositions that solidifies claim 6.
16, the product that obtains by the curable compositions that solidifies claim 7.
17, use the goods of the powder paint compositions coated of claim 3 or 4.
18, use the goods of the powder paint compositions coated of claim 5.
19, use the goods of the powder paint compositions coated of claim 6.
20, use the goods of the powder paint compositions coated of claim 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82718492A | 1992-01-28 | 1992-01-28 | |
| US07/827,184 | 1992-01-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1075727A true CN1075727A (en) | 1993-09-01 |
Family
ID=25248518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93102369A Pending CN1075727A (en) | 1992-01-28 | 1993-01-28 | Modified epoxy resin composition, the coating composition of curable compositions and low gloss |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0624172A1 (en) |
| JP (1) | JPH07503491A (en) |
| KR (1) | KR950700342A (en) |
| CN (1) | CN1075727A (en) |
| AU (1) | AU3596293A (en) |
| BR (1) | BR9305824A (en) |
| CA (1) | CA2126984A1 (en) |
| NO (1) | NO942795L (en) |
| WO (1) | WO1993015123A1 (en) |
| ZA (1) | ZA93618B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010078690A1 (en) * | 2009-01-06 | 2010-07-15 | Dow Global Technologies Inc. | Metal stabilizers for epoxy resins and dispersion process |
| WO2010078689A1 (en) * | 2009-01-06 | 2010-07-15 | Dow Global Technologies Inc. | Metallic compounds in non-brominated flame retardant epoxy resins |
| WO2010078688A1 (en) * | 2009-01-06 | 2010-07-15 | Dow Global Technologies Inc. | Metal stabilizers for epoxy resins |
| CN101952374B (en) * | 2008-01-25 | 2014-06-04 | 阿克佐诺贝尔国际涂料股份有限公司 | Powder coating compositions having a substantially non-zinc containing primer |
| CN105623583A (en) * | 2016-03-02 | 2016-06-01 | 苏州玛琦电子科技有限公司 | One-component epoxy encapsulating compound |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1310534A1 (en) * | 2001-11-07 | 2003-05-14 | Sigma Coatings S.A. | Treating primer for coil coating |
| JP2013108011A (en) * | 2011-11-22 | 2013-06-06 | Mitsubishi Chemicals Corp | Epoxy resin solution, epoxy resin composition, hardened material and adhesive |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8712121D0 (en) * | 1987-05-22 | 1987-06-24 | Dow Chemical Rheinwerk Gmbh | Film-forming resin compositions |
| US4820784A (en) * | 1988-01-13 | 1989-04-11 | The Dow Chemical Company | Modified advanced epoxy resins |
-
1993
- 1993-01-27 WO PCT/US1993/000747 patent/WO1993015123A1/en not_active Application Discontinuation
- 1993-01-27 CA CA002126984A patent/CA2126984A1/en not_active Abandoned
- 1993-01-27 JP JP5513418A patent/JPH07503491A/en active Pending
- 1993-01-27 AU AU35962/93A patent/AU3596293A/en not_active Abandoned
- 1993-01-27 EP EP93904686A patent/EP0624172A1/en not_active Withdrawn
- 1993-01-27 BR BR9305824A patent/BR9305824A/en not_active Application Discontinuation
- 1993-01-28 CN CN93102369A patent/CN1075727A/en active Pending
- 1993-01-28 ZA ZA93618A patent/ZA93618B/en unknown
-
1994
- 1994-07-27 KR KR1019940702580A patent/KR950700342A/en not_active Application Discontinuation
- 1994-07-27 NO NO942795A patent/NO942795L/en unknown
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101952374B (en) * | 2008-01-25 | 2014-06-04 | 阿克佐诺贝尔国际涂料股份有限公司 | Powder coating compositions having a substantially non-zinc containing primer |
| WO2010078690A1 (en) * | 2009-01-06 | 2010-07-15 | Dow Global Technologies Inc. | Metal stabilizers for epoxy resins and dispersion process |
| WO2010078689A1 (en) * | 2009-01-06 | 2010-07-15 | Dow Global Technologies Inc. | Metallic compounds in non-brominated flame retardant epoxy resins |
| WO2010078688A1 (en) * | 2009-01-06 | 2010-07-15 | Dow Global Technologies Inc. | Metal stabilizers for epoxy resins |
| CN102272228A (en) * | 2009-01-06 | 2011-12-07 | 陶氏环球技术有限责任公司 | Metal stabilizers for epoxy resins |
| CN102272228B (en) * | 2009-01-06 | 2013-04-17 | 陶氏环球技术有限责任公司 | Metal stabilizers for epoxy resins |
| CN105623583A (en) * | 2016-03-02 | 2016-06-01 | 苏州玛琦电子科技有限公司 | One-component epoxy encapsulating compound |
Also Published As
| Publication number | Publication date |
|---|---|
| NO942795D0 (en) | 1994-07-27 |
| KR950700342A (en) | 1995-01-16 |
| AU3596293A (en) | 1993-09-01 |
| NO942795L (en) | 1994-07-27 |
| WO1993015123A1 (en) | 1993-08-05 |
| CA2126984A1 (en) | 1993-08-05 |
| EP0624172A1 (en) | 1994-11-17 |
| JPH07503491A (en) | 1995-04-13 |
| BR9305824A (en) | 1997-02-18 |
| ZA93618B (en) | 1994-07-28 |
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