CN1074919A - Modified epoxy resin composition, solidification compound and coatings with low gloss finish composition - Google Patents
Modified epoxy resin composition, solidification compound and coatings with low gloss finish composition Download PDFInfo
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- CN1074919A CN1074919A CN93100906A CN93100906A CN1074919A CN 1074919 A CN1074919 A CN 1074919A CN 93100906 A CN93100906 A CN 93100906A CN 93100906 A CN93100906 A CN 93100906A CN 1074919 A CN1074919 A CN 1074919A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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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- Epoxy Resins (AREA)
Abstract
Has bigger stability in storage by adding oxide compound, oxyhydroxide, carbonate or the organic carboxylate of periodic table of elements IA, IIA, IIB, IIIA, VIB or VIII family metal, can make the epoxy powder coating that is used for the low gloss Application Areas that contains as the carbonyl bearing polymer of low gloss additives.
Description
The present invention relates to modified epoxy resin composition, its solidification compound and coatings with low gloss finish composition.
The powder coating of being made up of Resins, epoxy has stronger gloss usually.Need coatings with low gloss finish in some applications.Importantly, the prescription of coatings with low gloss finish also should formulation for coating material ought to need to store whole during in have stable glossiness.
Davis is at US4, discloses a kind of coating composition in 419,495, and it contains Resins, epoxy and as partly solidified at least dose polymkeric substance, this polymkeric substance contains the group with the Resins, epoxy reaction.It is said that this coating composition has low gloss.Though this coating has low gloss really, its storage time is shorter.This means that this coating composition storage time is long more, the gloss of resulting coating is high more.Glossy reduce refer to by containing similar epoxy substituting group but do not contain that the gloss of the coating that any multipolymer that has with the group of epoxy reaction makes compares.
Therefore, need a kind of modified epoxy resin composition, it contains the polymkeric substance that has with the polymeric groups of epoxy reaction, and when being mixed with coating composition, said composition its stability in storage for the glossiness of resulting coating is improved.The meaning that stability in storage improves be with preparation after the glossiness of 25 ℃ of coating that made by this formulation for coating material after storing 28 days is down making preparation in one hour the change of coating gloss degree be no more than 20% of initial glossiness.
A kind of form of the present invention relates to a kind of improvement of modified epoxy resin composition, and said composition comprises
(A) at least a Resins, epoxy on average contains the epoxy group(ing) of adjacency more than and contain at least one aromatic nucleus in its main chain in its numerous molecule;
(B) by at least a polymkeric substance of one or more ethylenically unsaturated monomer preparations, wherein at least a this monomer contains the carboxylic acid group; Wherein improve and be in said composition, to add
(C) at least a stabilizer compounds of stabilization amount, this compound are oxide compound, oxyhydroxide, carbonate or the organic carboxylate of periodic table of elements I A, II A, II B, III A, VI B or VIII family metal.
Another kind of form of the present invention relates to a kind of improvement of the composition that is suitable for use as epoxy curing agent, and said composition comprises:
(1) at least a polymkeric substance that makes by one or more ethylenically unsaturated monomers, wherein at least a this monomer contains hydroxy-acid group; With
(2) at least a this curing agent for epoxy resin, this solidifying agent is different from component (1); Wherein said improvement is to add in this curing agent composition
(3) at least a stabilizer compounds of stabilization amount, this compound are oxide compound, oxyhydroxide, carbonate or the organic carboxylate of periodic table of elements I A, II A, II B, III A, VI B or VIII family metal.
Another form of the present invention relates to a kind of improvement of solidification compound, and said composition comprises
(A) per molecule on average contains the epoxy group(ing) of adjacency more than and contain at least a Resins, epoxy of at least one aromatic ring in its main chain; With
(B) by at least a polymkeric substance of one or more ethylenically unsaturated monomer preparations, wherein at least a this monomer contains the carboxylic acid group;
(D) solidifying agent of at least a component (A), this solidifying agent both be different from component (B) and also be different from component (B) and pre-reaction thing (C);
Wherein said improvement is to add in said composition
(C) at least a stabilizer compounds of stabilization amount, this compound are the salt of oxide compound, oxyhydroxide, carbonate or the organic carboxyl acid of periodic table of elements I A, II A, II B, III A, VI B or VIII family metal.
Another form of the present invention relates to a kind of improvement of powder paint compositions, and said composition comprises
(A) per molecule on average contains the epoxy group(ing) of adjacency more than and contain at least a Resins, epoxy of at least one aromatic ring in its main chain;
(B) by at least a polymkeric substance of one or more ethylenically unsaturated monomer preparations, wherein at least a this monomer contains the carboxylic acid group; With
(D) solidifying agent of at least a component (A), this solidifying agent both be different from component (B) and also be different from component (B) and pre-reaction thing (C); With
(E) at least a or multiple annexing ingredient comprises pigment, filler, flow control agent, homogenizing auxiliary agent or other additive;
Wherein said improvement is to add in said composition
(C) at least a stabilizer compounds of stabilization amount, this compound are oxide compound, oxyhydroxide, carbonate or the organic carboxylate of periodic table of elements I A, II A, II B, III A, VI B or VIII family metal.
Another form of the present invention relates to by solidifying the product that above-mentioned solidification compound produces.
Another form of the present invention relates to the goods that applied by aforementioned coating composition.
The present invention can suitably comprise said components, is made up of said components, or is made up of said components substantially.
Here illustrative disclosed the present invention can not implement under the situation of the concrete open or any component enumerated of institute here easily, and arbitrary compound can contain or not contain any substituting group of specifically not mentioning here.
Here the data of the relevant periodic table of elements is provided by Sargent-Welch Scientific company, and its catalog number (Cat.No.) is S-18806.
In composition of the present invention, all components can blend simultaneously of any suitable method or mixing.
Use another kind of method, composition of the present invention can be by with arbitrary component: Resins, epoxy, the Preblend blend of carboxylic polymkeric substance or stablizer and all the other two components and preparing.
Use another kind of method in addition, composition of the present invention can prepare by a kind of pre-reaction thing blend Resins, epoxy and carboxylic polymkeric substance and stablizer.
Blend can be finished by any appropriate method, as driedly mix, melt extrude, two roller Banbury mixer or other fusion fitting method, or the combination of these methods.
When by melt extruding preparation during composition, temperature of reaction should be the temperature that does not react between the carboxyl of the epoxy group(ing) of Resins, epoxy and carboxylic polymkeric substance.The temperature that melt extrudes blend should be 30 ℃-120 ℃, is more preferably 40 ℃-100 ℃, preferably 50 ℃-70 ℃.
In above-mentioned any blend method, blend should carry out the sufficiently long time so that resulting blend is even substantially.The basic meaning uniformly is thin equal-suspension, does not wherein have the individual particle even as big as finding out.
The preferred blend method of the carbonyl bearing polymer of carbonyl bearing polymer or ionomer formula (reaction product of carbonyl bearing polymer and stablizer) is in independent step that the carbonyl bearing polymer and the epoxy blend of carbonyl bearing polymer or ionomer formula is a kind of by the Resins, epoxy of carbonyl bearing polymer modification to form.The advantage of this method is, with directly be blended into the powder coating prescription in compare carbonyl bearing polymer and be distributed in the Resins, epoxy more equably.In addition, be preferably under the condition that does not cause epoxy group(ing) and acid-base reaction carbonyl bearing polymer blend with Resins, epoxy and carbonyl bearing polymer or ionomer formula.This blending temperature should be 30 ℃-120 ℃, is more preferably 40 ℃-100 ℃, preferably 50 ℃-70 ℃.
When preparation solidification compound and powder paint compositions, all components can add separately, blend or melt extrude then, or with other method mixing or blend, or mixing is used in combination with blend.But, preferably earlier Resins, epoxy, carbonyl bearing polymer and stablizer are made Preblend, and this carbonyl bearing polymer and stablizer with epoxy blend before blend in advance or reaction in advance, early than with all the other the component blend in this Preblend and the composition.
In solidification compound of the present invention, the consumption of epoxy resin ingredient (A) is 66-99% by the gross weight of Resins, epoxy (A) and carbonyl bearing polymer (B), better is 80-96%, is more preferably 80-92%.
In solidification compound of the present invention, the consumption of carbonyl bearing polymer component (B) is 1-33% by the gross weight of epoxy resin ingredient (A) and carbonyl bearing polymer component (B), better is 4-20%, is more preferably 8-20%.
In solidification compound of the present invention, the amount of another kind of curing agent component (D) depends on used concrete solidifying agent.Usually the consumption of this another solidifying agent should make this curing agent component (D) add that the ratio of the equivalent of the equivalent of carbonyl bearing polymer or its ionomer component (B) and component (A) institute ring-containing oxide is 0.8: 1-3: 1.Better be 0.9: 1-2.5: 1.Be more preferably 1: 1-2: 1.
In solidification compound of the present invention, the consumption of stabilizer component (C) should be enough to make the positively charged ion of I A, II A in the periodic table of elements contained in the stabilizer component (C), II B, III A, VI or VIII family element replace 4-100%, better be 8-50%, be more preferably the hydrogen atom that contains in the carbonyl bearing polymer component (B) of 8-20%.
In curing agent composition of the present invention, the consumption of carbonyl bearing polymer component (1) is 1-99% by the gross weight of component (1) and (2), better is 3-96%, is more preferably 25-90%.
In curing agent composition of the present invention, the consumption of another kind of or different curing agent component (2) is 99-1% by the gross weight of component (1) and (2), better is 97-4%, is more preferably 75-10%.
In curing agent composition of the present invention, the consumption of stabilizer component (3) should be enough to make the positively charged ion of wherein contained periodic table of elements I A, II A, II B, III A, VI B or VIII family element to replace 4-100%, better be 8-50%, be more preferably contained hydrogen atom in the carboxyl of component (1) of 8-20%.
In curing agent composition of the present invention, promotor of using or catalyst consumption are 0.01-2% by the gross weight of solidifying agent, stabilizer component and promotor or catalyzer as required, better are 0.1-1.5%, are more preferably 0.2-0.8%.
Curing agent composition of the present invention can or melt extrude all components by simple blend and make.Method is will contain the salt of the polymeric constituent (1) of carboxyl or component (B) and periodic table of elements I A, II A, II B, III A, VI B or VIII family metal or oxide component (3) or component (C) earlier to react in advance, and then with other component blend.
By blend, mix, melt extrude or the combination of these methods can be prepared solidification compound.
Curing agent composition normally 30 ℃-200 ℃, better be 50 ℃-150 ℃, be more preferably 70 ℃ of-130 ℃ of reactions and be enough to form the time of homogeneous product and make, usually within 15 seconds to 2 hours, this depends on that each component is blend how.If when the preparation composition, use extrusion machine, use 15 seconds to 2 minutes short period usually.If use batch reactor or blending machine, it was longer then to prepare the used time of composition, as 5 minutes to 2 hours.
With the epoxy resin ingredient blend before or after, there is no need to remove the by product of carbonyl bearing polymer component and stabilizer component reaction.But if necessary, by making composition place under the vacuum, also when placing vacuum, (being generally room temperature as required to not being higher than 120 ℃ in the temperature of not damaging composition, be not higher than 100 ℃, be more preferably be not higher than 70 ℃) following heating combination, can remove by product at an easy rate.Pressure can be 0-760, better is 0-200, is more preferably the absolute Hg of 0-60mm.
Resins, epoxy
Here the suitable epoxy that can be used as component (A) comprises the Resins, epoxy that contains at least one aromatic ring in its main chain.
Specially suitable Resins, epoxy comprises, for example the glycidyl ether of following composition; Dihydric phenol, bis-phenol, phenol-or substituted phenol-Novolac resin, dihydric phenol or bis-phenol and per molecule contain the adducts, phenol of the epoxy alkane of 2-4 carbon atom-or the mixture of substituted phenol-unsaturated hydrocarbons resin or any two or more these compounds; Wherein illustrated Resins, epoxy per molecule on average contains more than one glycidyl ether group.These compounds also can contain substituting group, and as saturated aliphatic hydrocarbon, aliphatic unsaturated hydrocarbon comprises halogen, nitro, cyano group or their mixture of chlorine, bromine, fluorine, iodine.Equally, hydrocarbon substituent can be comprised that also halogen, nitro, cyano group or their mixture of chlorine, bromine, fluorine, iodine replace.These compounds can not contain any or multiple this substituting group according to situation yet.And this compound and replacement hydrocarbon can contain any substituting group of specifically not enumerating here.Equally, this compound and replacement hydrocarbon also can not contain any substituting group of specifically not enumerating here.
Preferably Resins, epoxy comprises, for example the glycidyl ether of following compound: Resorcinol, youngster's phenol, Resorcinol, dihydroxyphenyl propane, Bisphenol F, bis-phenol K, bisphenol S, fluorenes, phenol-Novolac resin, cresols-formaldehyde varnish resin, phenol-dicyclopentadiene resin, phenol-dicyclopentadiene higher oligomers resin, cresols-dicyclopentadiene resin, cresols-dicyclopentadiene higher oligomers resin; The adducts of the mixture of Resorcinol, youngster's phenol, Resorcinol, dihydroxyphenyl propane, Bisphenol F, bis-phenol K, bisphenol S or fluorenes and oxyethane, propylene oxide or butylene oxide ring or this class epoxy alkane; Or the mixture of two or more these glycidyl ethers.Any above-mentioned glycidyl ether that each aromatic ring contains 1-2 halogen atom (preferably bromine atoms) also is suitable.
The equivalent of Resins, epoxy of the present invention better is 200-2000, is more preferably 500-955, preferably 575-820.This equivalent is (even in fact the containing substituting group) that does not have substituting group to calculate on the aromatic ring according to Resins, epoxy.
The polymkeric substance that contains the carboxylic acid group
The suitable polymers that is made and can be used as component (B) or (1) by one or more ethylenically unsaturated monomers (wherein at least a this monomer contains the carboxylic acid group) here comprises that for example one or more have the alpha-olefin of 2-10 carbon atom and the partly multipolymer of acid of one or more ethylenically unsaturated carboxylic acids or binary ethylenically unsaturated carboxylic acids.
Specially suitable alpha-olefin comprises that for example the mixture of ethene, propylene, butylene, amylene, hexene, heptene, nonene, decene or any two or more alpha-olefins better is an ethene.
Specially suitable ethylenically unsaturated carboxylic acids comprises, for example vinylformic acid, methacrylic acid, toxilic acid, fumaric acid or methylene-succinic acid.Better be vinylformic acid and methacrylic acid, preferably vinylformic acid.
Specially suitable half ester comprises the C of toxilic acid, fumaric acid or methylene-succinic acid
1-C
10, better be C
1-C
6, be more preferably C
1-C
4The hydrocarbon half ester.More specially suitable is methyl, ethyl, propyl group, butyl, amyl group or the hexyl half ester of this class acid.
Metal oxide, oxyhydroxide, carbonate or carboxylate salt
Appropriate oxide, oxyhydroxide, carbonate or the organic carboxylate of periodic table of elements I A, II A, II B, III A, VI B or VIII family metal is at (the 7300Linder Ave of Sargent-Welch Scientific company, Skokie, IL60070) catalog number (Cat.No.) in the catalogue of being announced is Si-8806.
Specially suitable oxide compound, carbonate or organic carboxylate comprise, sodium oxide for example, Lithium Oxide 98min, potassium oxide, zinc oxide, calcium oxide, magnesium oxide, nickel oxide, aluminum oxide, chromic oxide, yellow soda ash, Quilonum Retard, salt of wormwood, zinc carbonate, lime carbonate, magnesiumcarbonate, nickelous carbonate, aluminium carbonate, chromium carbonate, or per molecule contains 1-30, better be 1-18, be more preferably the sodium of the alicyclic or fragrant organic carboxyl acid of the saturated or unsaturated aliphatic of 1-2 carbon atom, lithium, potassium, zinc, calcium, magnesium, nickel, aluminium or chromic salts, or the mixture of any two or more these compounds.Specially suitable this class carboxylate salt comprises sodium formiate, lithium formate, potassium formiate, zinc formate, calcium formiate, magnesium formiate, nickel formate, al formate, sodium acetate, lithium acetate, potassium acetate, zinc acetate, lime acetate, magnesium acetate, nickelous acetate, aluminum acetate, Sodium Propionate, the propionic acid lithium, potassium propionate, zinc propionate, calcium propionate, propionic acid magnesium, propionic acid nickel, propionic acid aluminium, sodium oleate, the oleic acid lithium, potassium oleate, zinc oleate, magnesium oleate, oleic acid nickel, aluminium oleate, sodium stearate, lithium stearate, potassium stearate, Zinic stearas, calcium stearate, Magnesium Stearate, nickel stearate, aluminum stearate, or the mixture of any two or more these compounds.
Preferred metallic compound comprises carbonate, acetate and the stearate of sodium, potassium, zinc and calcium, zinc oxide and zinc hydroxide, or the mixture of two or more these compounds.
Other solidifying agent
Be applicable to that except that carboxylic polymkeric substance or its ionomer the solidifying agent in curing agent composition or solidification compound or the powder paint compositions comprises that guanidine, biguanides, aliphatic amine, aromatic amine, per molecule on average contain compound, the aliphatic series of 1 above phenol or hydroxyl, cyclic aliphatic or aromatics binary or polycarboxylic acid or acid anhydrides, or the mixture of two or more these class solidifying agent.
The specially suitable solidifying agent that can be used as component (D) or (2) here comprises that Dyhard RU 100, adjacent toluene guanyl guanidine, acid functional polyester, per molecule contain the compound of more than one phenolic group, or the mixture of any two or more these class solidifying agent.Preferred solidifying agent is a Dyhard RU 100.
The actual amount of solidifying agent depends on used concrete solidifying agent.Usually the consumption of solidifying agent should make this solidifying agent and contain the carboxylic acid group polymer or the ratio of its ionomeric total yield and the equivalent of epoxide is 0.8: 1-3: 1, better be 0.9: 1-2.5: 1, be more preferably 1: 1-2: 1.
Promotor or catalyzer
Can promote that the suitable promotor of curing agent component and Resins, epoxy reaction or catalyzer for example comprise primary, the second month in a season or uncle's aliphatic series, cyclic aliphatic or aromatic amine, Lewis acid, or any two or more these class promotor or mixture of catalysts.
Specially suitable promotor or catalyzer comprise zinc oxide for example, imidazoles, substituted imidazole, with the imidazoles of the compound of ring-containing oxide such as single, double or polyglycidyl ether compound adduction, with the compound such as the substituted imidazole single, double or polyglycidyl ether compound adduction of ring-containing oxide, or any two or more these class promotor or mixture of catalysts.Preferred promotor or catalyzer be glyoxal ethyline, with the glyoxal ethyline of the diglycidylether adduction of dihydroxyphenyl propane, or any two or more these class promotor or mixture of catalysts.
The amount of promotor depends on used concrete promotor and solidifying agent.By the gross weight of all solidifying agent, stabilizer component and promotor or catalyzer, the amount of used promotor is generally 0.01-2%, better is 0.1-1.5%, is more preferably 0.2-0.8%(weight).
Filler
Here the available suitable filler comprises for example mineral filler, as inorganic oxide, carbonate vitriol or the silicate of periodic table of elements I A, II A, II B, III A, VI B or VIII family metal, or the mixture of two or more these class fillers.Preferred filler is the mixture of titanium oxide, lime carbonate, barium sulfate, Magnesium Silicate q-agent, strontium silicate or any two or more these class fillers.
Pigment
Here the available suitable pigments comprises for example any inorganic or pigment dyestuff that required color can be provided to composition, or the mixture of any two or more these class pigment.
Flowing regulator or flow control agent
Here available proper flow conditioning agent or flow control agent comprise for example acrylic copolymer, silicone, fluorocarbon, or the mixture of any two or more these class flowing regulators or control agent.Preferred conditioning agent or flow control agent are acrylic copolymer.
Levelling agent
Here the suitable levelling agent of available comprises for example bitter almond oil camphor.
Here random filler, pigment, flowing regulator or flow control agent that adds of available and levelling agent all use with actuating quantity, promptly are that coating provides the amount of desired properties to use with the special additive.This tittle will change with used concrete Resins, epoxy, solidifying agent and additive.
The consumption of filler generally is 0-60% by the gross weight of composition, better is 0-50%, is more preferably 2-35%.
The consumption of pigment generally is 0-50% by the gross weight of composition, better is 0-40%, is more preferably 2-35%.
The consumption of flowing regulator or flow control agent generally is 0-5% by the gross weight of composition, better is 0-3%, is more preferably 0-2%.
The consumption of levelling agent generally is 0-2% by the gross weight of composition, better is 0-1.5%, is more preferably 0-0.5%.
Following examples are illustrative explanations of the present invention, but they can not to be construed to be by any way its scope to be limited.Following component is used for embodiment and contrast experiment.
Resins, epoxy
Resins, epoxy A is the diglycidylether of dihydroxyphenyl propane with about 182-192 epoxide equivalent (EEW) and the new reaction product of dihydroxyphenyl propane.The novel epoxy resins that is produced has about 575-685 epoxide equivalent, and can be available from The Dow Chemical Company, and its commodity are called D.E。R
TM662。
Resins, epoxy B has the diglycidylether of dihydroxyphenyl propane of about 182-192 EEW and the new reaction product of dihydroxyphenyl propane.The EEW of the novel epoxy resins that is produced is about 730-820, and can be available from The Dow Chemical Company, and its commodity are called D.E。R
TM663U。
Carboxylic polymkeric substance
Carbonyl bearing polymer A is for containing about 80%(weight) ethene and 20%(weight) acrylic acid multipolymer, its acid equivalent (AEW) is 360, and melting index is that about 1300,125 ℃ fusion flow is about 65, can be available from The Dow Chemical Company, commodity are called PRIMACOR
TM5990.
CaPr
2For deriving from the pure calcium propionate of reagent of Eastman Kodak Company.
NaAc is the pure sodium acetate of reagent that derives from Aldrich Chemical Company.
ZnAc2 is the pure zinc acetate of reagent that derives from Aldrich Chemical Company.
ZnSl2 is the pure Zinic stearas of reagent that derives from Aldrich Chemical Company.
Other solidifying agent
Solidifying agent A is the commodity E-PON by name that derives from Shell Chemical Company
TMThe acceleration Dyhard RU 100 of P-108.
Solidifying agent B is the commodity D by name that derives from The Dow Chemical Company.E。H
TM41 acceleration Dyhard RU 100.
Flowing regulator
Flowing regulator A is the Moderez that derives from Synthron Chemicals
TMMFP.
Filler
BS-1 is the barium sulfate that derives from the commodity SparniteW-10 by name of Mountain Minerals.
BS-2 is the barium sulfate that derives from the commodity Barytes#1 by name of Pfizer.
Pigment
Pigment A is the carbon black that derives from the commodity Raven2000 by name of Columbia Chemicals.
Comparative experiment A
1. preparation is by 8.0%(weight) Resins, epoxy of carbonyl bearing polymer modification
In the 100mmBaker-Perkins twin screw extruder, be that 0.087: 1 carbonyl bearing polymer A and Resins, epoxy A can prepare modified epoxy by forcing machine melting mixing weight ratio in 90 ℃-110 ℃.Product is expressed on the cooling zone with sheet form, then crushing.
2. preparation powder coating
Derive from 2 in above-mentioned 1 by melting mixing, 000g modified epoxy, 80g solidifying agent B and 26g flowing regulator A can prepare the powder coating prescription.Dried blend by these components of making of vibration in plastics bag is a melting mixing in the BussConduxPLK46 forcing machine, and this forcing machine has the screw rod that temperature is 70 ℃ district 1, district 2 that temperature is 90 ℃ and 70 ℃, 200rpm.With cooling roller extrudate is pressed into thin slice, after air cooling, is ground into fine powder, and sieve with 150 order brass sieves (105um opening) with the BrinkmannZM-1 pulverizer.The part powder applies in two days after melting mixing, and the part powder is then at room temperature aging to apply after 43 days.With GemaType710 electrostatic spray gun (6okv) with powder spray to the cold-rolled steel sheet of priming.To scribble the steel plate of powder in 180 ℃ of bakings 15 minutes and air cooling.
Embodiment 1
The modified epoxy, 80g solidifying agent B, 26g flowing regulator A and the 80gCaPr2 stablizer that derive from Comparative experiment A-1 by melting mixing 2000g prepare the powder coating prescription.By with the same method of Comparative experiment A-2 in same time preparation and test composition.
Embodiment 2
The modified epoxy, 80g solidifying agent B, 26g flowing regulator A and the 240gCaPr2 stablizer that derive from Comparative experiment A-1 by melting mixing 2000g are prepared the powder coating prescription, by with the same method of Comparative experiment A-2 in same time preparation and test composition.
Contrast experiment B
1. 20%(weight is used in preparation) Resins, epoxy of carbonyl bearing polymer modification
By melting mixing 2000g carbonyl bearing polymer A and 8,000g Resins, epoxy B prepares modified epoxy.Dried blend by these components of making of vibration in plastics bag is a melting mixing in the BussConduxPLK46 forcing machine, and this forcing machine has the screw rod that temperature is 70 ℃ the district 2 in 1,80 ℃ in district and 70 ℃, 200rpm.The modified epoxy extrudate is pressed into thin slice with cooling roller, and air cooling is also pulverized.
2. preparation powder coating
Derive from above-mentioned 1 other Resins, epoxy B, 48g solidifying agent A and the 10.06g flowing regulator A of modified epoxy, 600g by melting mixing 6000g and prepare the powder coating prescription.Dried blend melting mixing in the BussConduxPLK46 forcing machine by vibrating these components prepared in plastics bag, this forcing machine have the screw rod that temperature is 70 ℃ the district 2 in 1,90 ℃ in district and 70 ℃, 200rpm.With cooling roller extrudate is pressed into thin slice, is ground into fine powder with the BrinkmannZM-1 pulverizer after the air cooling, and sieve with 150 order brass sieves (105um opening).The part powder applies in two days after melting mixing, and another part powder applies after aging 23 hours at 36 ℃.With the Gema rifle with powder at electrostatic spray to the cold-rolled steel sheet of priming.With the steel plate that scribbles powder in 180 ℃ of bakings 15 minutes, and air cooling.
Embodiment 3
Other Resins, epoxy B, 48g solidifying agent A, 10.06g flowing regulator A and the 12gCaPr2 stablizer of modified epoxy, 600g that derives from contrast experiment B-1 by melting mixing 600g prepared the powder coating prescription.By with the same method of contrast experiment B-2 in same time preparation and test composition.
Embodiment 4
Other Resins, epoxy B, 48g solidifying agent A, 10.06g flowing regulator A and the 24gCaPr2 stablizer of modified epoxy, 600g that derives from contrast experiment B-1 by melting mixing 600g prepared the powder coating prescription.By with the same method of contrast experiment B-2 in same time preparation and test composition.
Embodiment 5
Other Resins, epoxy B, 48g solidifying agent A, 10.06g flowing regulator A and the 48gCaPr2 stablizer of modified epoxy, 600g that derives from contrast experiment B-1 by melting mixing 600g prepared the powder coating prescription.By with the same method of contrast experiment B-2 in same time preparation and test composition.
Contrast experiment C
1. 20%(weight is used in preparation) Resins, epoxy of carbonyl bearing polymer modification
Identical with contrast experiment B-1.
2. preparation powder coating
Prepare the powder coating prescription by the other Resins, epoxy B of modified epoxy, 600g described in the melting mixing 600g above-mentioned 1,48g solidifying agent A, 245gBS-2 filler, 22.97g pigment A and 15.31g flowing regulator A.By dried blend melting mixing in the BussCondulPLK46 forcing machine of these components of making of vibration in plastics bag, this forcing machine has the screw rod that temperature is 70 ℃ the district 2 in 1,90 ℃ in district and 70 ℃, 200rpm.With cooling roller extrudate is pressed into thin slice, air cooling is ground into fine powder with the BrinkmannZM-1 pulverizer with it and also sieves with 150 order brass sieves.The part powder applied within after the melting mixing 1 day, and the part powder applies after aging 20 hours at 40 ℃.With the Geme rifle powder static electricity is sprayed on the cold-rolled steel sheet of priming.The steel plate that scribbles powder is in 180 ℃ of bakings 15 minutes and air cooling.
Embodiment 6
Other Resins, epoxy B, 48g solidifying agent A, 247gBS-2 filler, 23.19g pigment A, 15.46g flowing regulator A and the 12gCaPr2 stablizer of modified epoxy, 600g that derives from contrast experiment C-1 by melting mixing 600g prepared the powder coating prescription.Prepare at one time and test composition by the method identical with contrast experiment C-2.
Embodiment 7
Other Resins, epoxy B, 48g solidifying agent A, 250gBS-2 filler, 23.41g pigment A and 15.61g flowing regulator A and the 24gCaPr2 stablizer of modified epoxy, 600g that derives from contrast experiment C-1 by melting mixing 600g prepared the powder coating prescription.Prepare at one time and test composition by the method identical with contrast experiment C-2.
Embodiment 8
Other Resins, epoxy B, 48g solidifying agent A, 254gBS-2 filler, 23.85g pigment A and 15.90g flowing regulator A and the 48gCaPr2 stablizer of modified epoxy, 600g that derives from contrast experiment C-1 by melting mixing 600g prepared the powder coating prescription.Prepare at one time and test composition by the method identical with contrast experiment C-2.
Contrast experiment D
1. 15%(weight is used in preparation) Resins, epoxy of carbonyl bearing polymer modification
By melting mixing 1,800g carbonyl bearing polymer A and 10,200g Resins, epoxy B prepares modified epoxy.By dried blend melting mixing in the BussConduxPLK46 forcing machine of these components of making of vibration in plastics bag, this forcing machine has the screw rod that temperature is 70 ℃ the district 2 in 1,80 ℃ in district and 70 ℃, 212rpm.With cooling roller modified epoxy is pressed into thin slice, pulverizes after the air cooling.
2. preparation powder coating
Derive from top 1 other Resins, epoxy B, 72g solidifying agent A and the 18.9g flowing regulator A of modified epoxy, 600g by melting mixing 1200g, prepare the powder coating prescription.By dried blend melting mixing in the Buss-ConduxPLK46 forcing machine of these components of making of vibration in plastics bag, this forcing machine has the screw rod that temperature is 70 ℃ the district 2 in 1,90 ℃ in district and 70 ℃, 200rpm.With cooling roller extrudate is pressed into thin slice, air cooling is ground into fine powder with the BrinkmannZW-1 pulverizer, and sieves with 150 order brass sieves.The part powder applies in two days after melting mixing, partial coating is then at room temperature aging applied after 27 days.With Gema rifle electrostatic spray powder to the cold-rolled steel sheet of priming.With the steel plate that scribbles powder in 180 ℃ of bakings 15 minutes, and air cooling.
Embodiment 9
Derive from other Resins, epoxy B, 72g solidifying agent A, 19.2g flowing regulator A and the 31.2gCaPr2 stablizer of modified epoxy, 600g of contrast experiment D-1 by melting mixing 1200g, prepare the powder coating prescription.By preparing at one time and test composition with quadrat method with contrast experiment D-2.
Embodiment 10
Derive from other Resins, epoxy B, 72g solidifying agent A, 19.3g flowing regulator A and the 37.2gZnAc2 stablizer of modified epoxy, 600g of contrast experiment D-1 by melting mixing 1200g.By preparing at one time and test composition with quadrat method with contrast experiment D-2.
Embodiment 11
Other Resins, epoxy B, 72g solidifying agent A, 20.0g flowing regulator A and the 105.6gZnSt2 stablizer of modified epoxy, 600g that derives from contrast experiment D-1 by melting mixing 1200g prepared the powder coating prescription.By preparing at one time and test composition with quadrat method with contrast experiment D-2.
Contrast experiment E
1. 15%(weight is used in preparation) Resins, epoxy of carbonyl bearing polymer modification
Prepare modified epoxy by melting mixing 900g carbonyl bearing polymer A and 5100g Resins, epoxy B.By dried blend melting mixing in the BussConduxPLK46 forcing machine of these components of making of vibration in plastics bag, this forcing machine has the screw rod that temperature is 70 ℃ the district 2 in 1,80 ℃ in district and 70 ℃, 212rpm.With cooling roller extrudate is pressed into thin slice, after air cooling, is ground into fine powder, and sieve with 150 order brass sieves with the BrinkmannZM-1 pulverizer.The part powder apply within after the melting mixing 1 day, the part powder then applies after aging 24 hours at 40 ℃, some powder is then at room temperature aging to apply after 33 days.This powder is sprayed on the cold-rolled steel sheet of priming by the WagnerG100EPB electrostatic spray gun.The steel plate that powder spraying is crossed was in 180 ℃ of bakings 15 minutes, and air cooling.
Embodiment 12
A. the pre-reaction product for preparing carbonyl bearing polymer and metal-containing salt
At Werner and Pfteiderer(wp) in the 30mm twin screw extruder by melting mixing 11.7g/minCaPr2 stablizer and 270g/min carbonyl bearing polymer A, prepare the pre-reaction product (ionomer) of carbonyl bearing polymer A.The tube temperature is: distinguish 1,52 ℃; District 2-5,113-121 ℃.Extrude product by three-wire type mouth mould, be cut into 1/4 inch pellet after the water cooling.
B. 15%(weight is used in preparation) Resins, epoxy of carbonyl bearing polymer modification
Calcium by the carbonyl bearing polymer A that makes among the melting mixing 900gA is prepared modified epoxy from aggressiveness and 5100g Resins, epoxy B.Prepare composition by the method identical with the modified resin of contrast experiment E-1.
C. prepare powder coating
Derive from modified epoxy, 60g solidifying agent A, 300gBS-1 filler, 28.6g pigment A and the 19.1g flowing regulator A of top B by melting mixing 1500g, prepare the powder coating prescription.By preparing at one time and test composition with the same method of contrast experiment E-2.
Embodiment 13
A. the pre-reaction product for preparing carbonyl bearing polymer and metal-containing salt
By at Werner and Pfteiderer(wp) melting mixing 13.2g/minZnAc2 stablizer and 270g/min carbonyl bearing polymer A in the 30mm twin screw extruder, prepare the pre-reaction product (ionomer) of carbonyl bearing polymer A.The tube temperature is: distinguish 1,52 ℃; District 2-5,113-121 ℃.Extrude product by three-wire type mouth mould, be cut into 1/4 inch (6.35mm) pellet after the water cooling.
B. 15%(weight is used in preparation) Resins, epoxy of carbonyl bearing polymer modification
Zinc ionomer and 5100g Resins, epoxy B by melting mixing 900g carbonyl bearing polymer A prepare modified epoxy.By preparing composition with the same method of contrast experiment E-1.
C. prepare powder coating
Derive from modified epoxy, 60g solidifying agent A, 300gBS-1 filler, 28.6g pigment A and the 19.1g flowing regulator A of above-mentioned B by melting mixing 1500g, prepare the powder coating prescription.By preparing at one time and test composition with the same method of contrast experiment E-2.
Contrast experiment F
1. 15%(weight is used in preparation) Resins, epoxy of carbonyl bearing polymer modification
Prepare modified epoxy by melting mixing 600g carbonyl bearing polymer A and 3400g Resins, epoxy B.By dried blend melting mixing in the BussConduxPLK46 forcing machine of these components of making of vibration in plastics bag, this forcing machine has the screw rod that temperature is 70 ℃ the district 2 in 1,80 ℃ in district and 70 ℃, 200rpm.Extrudate is pressed into thin slice through cooling roller, is ground into fine powder with the BrinkmannZM-1 pulverizer after the air cooling, and sieves with 150 order brass sieves.The part powder applies within one day after in melting mixing, the part powder then applies after aging 24 hours at 40 ℃, powder by Wagner rifle electrostatic spray to the cold-rolled steel sheet of priming.This steel plate is in 180 ℃ of baking air coolings after 15 minutes.
Embodiment 14
A. the pre-reaction product for preparing carbonyl bearing polymer and metal-salt
By melting mixing 8.8g/minZnAc2 stablizer in the WP30mm twin screw extruder and 355g/min carbonyl bearing polymer A, prepare the pre-reaction product (ionomer) of carbonyl bearing polymer A.The tube temperature is: distinguish 1,53 ℃; District 2-5,109-117 ℃.Product is extruded through three-wire type mouth mould, is cut into 1/4 inch (6.35mm) pellet after the water cooling.
B. 15%(weight is used in preparation) Resins, epoxy of carbonyl bearing polymer modification
Zinc ionomer and 3400g Resins, epoxy B by the carbonyl bearing polymer A that makes among the A above the melting mixing 600g prepare modified epoxy.By preparing composition with the same mode of contrast experiment F-1 modified resin.
C. prepare powder coating
By melting mixing 1,500g derives from modified epoxy, 60g solidifying agent A, 300gBS-1 filler, 28.6g pigment A and the 19.1g flowing regulator A of top B, prepares the powder coating prescription.By preparing at one time and test composition with the same method of contrast experiment F-2.
Embodiment 15
A. the pre-reaction product for preparing carbonyl bearing polymer and metal-salt
By melting mixing 17.1g/minZnAc2 stablizer in the WP30mm twin screw extruder and 355g/min carbonyl bearing polymer A, prepare the pre-reaction product (ionomer) of carbonyl bearing polymer A.The tube temperature is: distinguish 1,51 ℃; District 2-5,105-116 ℃.Product through three-wire type mouth mould extrude and air cooling after be cut into 1/4 inch (6.35mm) pellet.
B. 15%(weight is used in preparation) Resins, epoxy of carbonyl bearing polymer modification
Zinc ionomer and 3400g Resins, epoxy B by melting mixing 600g carbonyl bearing polymer A prepare modified epoxy.By preparing composition with the same method of contrast experiment F-1 modified resin.
C. prepare powder coating
Derive from modified epoxy, 60g solidifying agent A, 300gBS-1 filler, 28.6g pigment A and the 19.1g flowing regulator A of B by melting mixing 1500g, make the powder coating prescription.By preparing at one time and test composition with the same method of contrast experiment F-2.
Embodiment 16
A. prepare powder coating
Derive from modified epoxy, 60g solidifying agent A, 300gBS-1 filler, 28.6g pigment A and 19.1g flowing regulator A and the 11.25gZnAc2 stablizer of contrast experiment F1 by melting mixing 1500g, prepare the powder coating prescription.By preparing at one time and test composition with the same method of contrast experiment F-2.
Contrast experiment G
1. the preparation 15%(weight) Resins, epoxy of carbonyl bearing polymer modification
In the 100mmBaker-Perkins twin screw extruder, by with carbonyl bearing polymer A and Resins, epoxy B in 0.85: 1 ratio in 90 ℃ of-110 ℃ of melting mixing, prepare the modified resin product and be expressed on the cooling zone with laminar, pulverize then.
2. preparation powder coating
By melting mixing 1,500g derives from top 1 modified epoxy, 60g solidifying agent A, 300gBS-1 filler, 28.6g pigment A and 19.1g flowing regulator A, makes the powder coating prescription.The dried blend of the said components that makes by vibration in plastics bag melting mixing in the BussConduxPLK46 forcing machine, this forcing machine have the screw rod that temperature is 70 ℃ the district 2 in 1,80 ℃ in district and 70 ℃, 200rpm.Extrudate is pressed into thin slice with cooling roller, is ground into fine powder with the BrinkmannZM-1 pulverizer after the air cooling, and sieves with 150 order brass sieves.The part powder applies in 1 day after melting mixing, another part powder then applies after aging 24 hours at 40 ℃, with the Wagner rifle with electrostatic powder spraying to the cold-rolled steel sheet of priming.In 180 ℃ of baking air coolings after 15 minutes.
Embodiment 17
A. the pre-reaction product for preparing carbonyl bearing polymer and metal-salt
In the WP30mm twin screw extruder,, prepare the pre-reaction product (ionomer) of carbonyl bearing polymer A by melting mixing 22.5g/minNaAc stablizer and 355g/min carbonyl bearing polymer A.The tube temperature is: distinguish 1,50 ℃; District 2-5,104-107 ℃.Product through three-wire type mouth mould extrude and water cooling after be cut into 1/4 inch (6.35mm) pellet.
B. 15%(weight is used in preparation) Resins, epoxy of carbonyl bearing polymer modification
Zinc ionomer and 3400g Resins, epoxy B by melting mixing 600g carbonyl bearing polymer A prepare modified epoxy.By preparing composition with the same method of contrast experiment F-1 modified resin.
C. prepare powder coating
By melting mixing 1,500g derives from modified epoxy, 60g solidifying agent A, 300gBS-1 filler, 28.6g pigment A and the 19.1g flowing regulator A of B, prepares the powder coating prescription.By preparing at one time and test composition with the same method of contrast experiment G-2.
Embodiment 18
A. the pre-reaction product for preparing carbonyl bearing polymer and metal-containing salt
Make the pre-reaction product (ionomer) of carbonyl bearing polymer A by melting mixing 47.3g/minZ-nAc2 stablizer in the WP30mm twin screw extruder and 355g/min carbonyl bearing polymer A.The tube temperature is: distinguish 1,48 ℃; District 2-5,105-113 ℃.Product through three-wire type mouth mould extrude and water cooling after be cut into the pellet of 1/4 inch (6.35mm).
B. 15%(weight is used in preparation) Resins, epoxy of carbonyl bearing polymer modification
Zinc ionomer and 3400g Resins, epoxy B by melting mixing 600g carbonyl bearing polymer A prepare modified epoxy.By preparing composition with the same method of the modified resin of contrast experiment F-1.
C. prepare powder coating
The modified epoxy, 60g solidifying agent A, 300gBS-1 filler, 28.6g pigment A and the 19.1g flowing regulator A that derive from B by melting mixing 1500g prepare the powder coating prescription.By preparing at one time and test composition with the same method of contrast experiment G-2.
Embodiment 19
A. prepare powder coating
By melting mixing 1,500g derives from modified epoxy, 60g solidifying agent A, 300gBS-1 filler, 28.6g pigment A, 19.1g flowing regulator and the 11.25gZnAc2 stablizer of contrast experiment G-1 and prepares the powder coating prescription.By preparing at one time and test composition with the same mode of contrast experiment G-2.
Embodiment 20
A. the pre-reaction product for preparing carbonyl bearing polymer and metal-containing salt
The pre-reaction product (ionomer) for preparing carbonyl bearing polymer A by melting mixing 48.2g/minZnSt2 stablizer in the WP30mm twin screw extruder and 355g/min carbonyl bearing polymer A.The tube temperature is: distinguish 1,56 ℃; District 2-5,128-139 ℃.Product through three-wire type mouth mould extrude with water cooling after be cut into the pellet of 1/4 inch (6.35mm).
B. 15%(weight is used in preparation) Resins, epoxy of carbonyl bearing polymer modification
Zinc ionomer and 3400g Resins, epoxy B by melting mixing 600g carbonyl bearing polymer A prepare modified epoxy.By preparing composition with the same method of the modified resin of contrast experiment F-1.
C. prepare powder coating
By melting mixing 1,500g modified epoxy, 60g solidifying agent A, 300gBS-1 filler, 28.6g pigment A and 19.1g flowing regulator A prepare the powder coating prescription.By preparing at one time and test composition with the same method of contrast experiment G-2.
Embodiment 21
A. the pre-reaction product for preparing carbonyl bearing polymer and metal-containing salt
By in the WP30mm twin screw extruder by the dried blend of the ion product (ionomer) of 0.0488: 1 about 4000gZnAc2 stablizer of weight ratio melting mixing and carbonyl bearing polymer A, prepare the pre-reaction product (ionomer) of carbonyl bearing polymer A.The tube temperature is: distinguish 1,44 ℃; District 2-5,103-111 ℃.The vacuum valve fixes on the absolute Hg of 20mm to remove by-product acetic acid.Product through three-wire type mouth mould extrude and water cooling after be cut into the pellet of 1/4 inch (6.35mm).
B. 15%(weight is used in preparation) Resins, epoxy of carbonyl bearing polymer modification
Zinc ionomer and 2500g Resins, epoxy B by the carbonyl bearing polymer A that makes among the melting mixing 21-A prepare modified epoxy.The dried blend of these components of making of vibration is molten mixtures in the BussConduxPLK46 forcing machine in plastics bag, and this forcing machine has the screw rod that temperature is 20 ℃ the district 2 in 1,70 ℃ in district and 20 ℃, 200rpm.The modified epoxy extrudate is pressed into thin slice with cooling roller, and air cooling is also pulverized.
C. prepare powder coating
Derive from modified epoxy, 62.9g solidifying agent A, 315gBS-1 filler, 30g pigment A, and the 20g flowing regulator A of 21-B, preparation powder coating prescription by melting mixing 1570g.Dried blend melting mixing in the Buss-ConduxPLK46 forcing machine of the said components that makes of vibration in plastics bag, this forcing machine have the screw rod that temperature is 50 ℃ the district 2 in 1,80 ℃ in district and 50 ℃, 200rpm.Extrudate is pressed into thin slice with cooling roller, is ground into powder with the BrinkmannZM-1 pulverizer after the air cooling.And sieve with 150 order brass sieves.The part powder applies in one day after in melting mixing.Another part powder then applies after aging 24 hours at 40 ℃.With the Wagner rifle with electrostatic powder spraying to cold-rolled steel sheet.In 180 ℃ of baking air coolings after 15 minutes.
Embodiment 22
A. the pre-reaction product for preparing carbonyl bearing polymer and metal-containing salt
In the WP30mm twin screw extruder,, prepare the pre-reaction product (ionomer) of carbonyl bearing polymer A by the dried blend of melting mixing 120.6gZnCo3 stablizer and 4324g carbonyl bearing polymer A.The tube temperature is: distinguish 1,46 ℃; District 2-5,105-111 ℃.The vacuum valve fixes on the absolute Hg of 20mm to remove water byproduct.Product through three-wire type mouth mould extrude with water cooling after be cut into the pellet of 1/4 inch (6.35mm).
B. 15%(weight is used in preparation) Resins, epoxy of carbonyl bearing polymer modification
Carbonyl bearing polymer A and 2550g Resins, epoxy B by melting mixing 22-A makes prepare modified epoxy.By preparing composition with the same method of embodiment 21-B.
C. prepare powder coating
Derive from modified epoxy, 62.7g solidifying agent A, 315gBS-1 filler, 30g pigment A and the 20g flowing regulator of 22-B by melting mixing 1570g, preparation powder coating prescription.By preparing composition with the same method of example 22-C.
Following table I is summed up being grouped into the embodiment and the contrast experiment that obtain simultaneously.
The table I
To general description by the embodiment of parallel embodiment grouping
Explanation
Parallel I group is used the epoxy tree of 8wt% carbonyl bearing polymer A modification
Transparent, the filling formulation not of fat.Calcium propionate as the prescription
Additive is tested on two levels.
Comparative experiment A * contrasts (not stabilization)
Contain the 3.66wt% calcium propionate in embodiment 1 prescription
Contain the 10.23wt% calcium propionate in embodiment 2 prescriptions
Parallel II group is used transparent, the filling formulation not of solidifying agent A.Hybrid ring
Epoxy resins is the carboxyl that contains of 0.1:0.9 by weight ratio
Polymer A and Resins, epoxy B form.Calcium propionate is as joining
The additive of side is tested on three levels.
Contrast experiment B* contrasts (not stabilization)
Contain the 0.94wt% calcium propionate in embodiment 3 prescriptions
Contain the 1.87wt% calcium propionate in embodiment 4 prescriptions
Contain the 3.67wt% calcium propionate in embodiment 5 prescriptions
Parallel III group is used black, 16% filling formulation of solidifying agent A.Mix
The cyclization epoxy resins is containing of 0.1:0.9 by weight ratio
Carboxyl copolymer A and Resins, epoxy B.Calcium propionate and epoxy
Identical in the weight ratio of resin and the II group.
Contrast experiment C* contrasts (not stabilization)
Contain the 0.78wt% calcium propionate in embodiment 6 prescriptions
Contain the 1.54wt% calcium propionate in embodiment 7 prescriptions
Contain the 3.02wt% calcium propionate in embodiment 8 prescriptions
Parallel IV group is used 15wt% carbonyl bearing polymer A and solidifying agent A
Transparent, the filling formulation not of the Resins, epoxy of modification.Propionic acid
Calcium, zinc acetate and Zinic stearas have identical normal metal
Ion.
Contrast experiment D* contrasts (not stabilization)
Contain the 1.62wt% calcium propionate in embodiment 9 prescriptions
Contain the 1.93wt% zinc acetate in embodiment 10 prescriptions
Contain the 5.29wt% Zinic stearas in embodiment 11 prescriptions
What black, the 16wt% of parallel V group use solidifying agent A filled joins
The side.Resins, epoxy is 0.15:0.85's by weight ratio
Carbonyl bearing polymer A or carbonyl bearing polymer A ionomer reach
Resins, epoxy B forms.
Contrast experiment E* contrasts (not stabilization)
Embodiment 12 is 0.16:1 by the equivalence ratio of metal ion and acidic group
Carbonyl bearing polymer A ionomer by the calcium propionate generation.
Embodiment 13 is 0.16:1 by the equivalence ratio of metal ion and acidic group
Carbonyl bearing polymer A ionomer by the zinc acetate generation.
Parallel VI group and V category are seemingly
Contrast experiment F* contrast, not stabilization
Embodiment 14 is that 0.08:1 is by second by the equivalence ratio of ion and acidic group
The carbonyl bearing polymer A ionomer that acid zinc produces
Embodiment 15 is that 0.16:1 is by second by the equivalence ratio of ion and acidic group
The carbonyl bearing polymer A ionomer that acid zinc produces.
Embodiment 16 presses the epoxy tree of 15wt% carbonyl bearing polymer A modification
Fat B meter adds the 0.5wt% zinc acetate in the prescription, make
The equivalence ratio of ion and acidic group is 0.16:1.
Parallel VII group and V category are seemingly
Control experiment G* contrast, not stabilization
Embodiment 17 is that 0.16:1 is by second by the equivalence ratio of ion and acidic group
The carbonyl bearing polymer A ionomer that acid sodium produces
Embodiment 18 is that 0.48:1 is by second by the equivalence ratio of ion and acidic group
The carbonyl bearing polymer A ionomer that acid zinc produces
Embodiment 19 presses the epoxy tree of 15wt% carbonyl bearing polymer A modification
Fat B meter adds the 1.55wt% zinc acetate in the prescription,
The equivalence ratio that makes ion and acidic group is 0.48:1.
Embodiment 20 is 0.16:1 by firmly by the equivalence ratio of ion and acidic group
The carbonyl bearing polymer A ionomer that resin acid zinc produces.
Parallel VIII group and V category are seemingly
Embodiment 21 is that 0.16:1 is by second by the equivalence ratio of ion and acidic group
The ionomer of the carbonyl bearing polymer that acid zinc produces.
Embodiment 22 is that 0.16:1 is by carbon by the equivalence ratio of ion and acidic group
The ionomer of the carbonyl bearing polymer that acid zinc produces.
* not embodiments of the invention
The table II
Fusion on Werner and Pfleiderer30mm forcing machine
The mixed ionomeric conclusive table of carbonyl bearing polymer that gets
1 Capr
2, calcium propionate; ZnAc
2, zinc acetate; NaAc, sodium acetate; ZnSt
2, Zinic stearas.
The equivalence ratio of 2 metal ions and acidic group.
3 metal ions are converted into the ionomeric percentage ratio of carbonyl bearing polymer.
4 can not use, and metal-salt and carbonyl bearing polymer ionomer have carried out pre-mixing, shown in reinforced rate be directed to mixture.
5 undetermineds.
The table III
The conclusive table of the modified epoxy of melting mixing preparation on forcing machine
* not the embodiment of the invention
1 Resins, epoxy A
2 carboxy-containing copolymer A
3 Resins, epoxy B
4 CaPr
2=calcium propionate, ZnAc
2=zinc acetate, NaAc=sodium acetate, ZnSt
2=Zinic stearas, ZnCO
3=zinc carbonate.
Table III (continuing)
* not the embodiment of the invention
1 Resins, epoxy B
2 carboxy-containing copolymer A
3 CaPr
2=calcium propionate, ZnAc
2=zinc acetate, NaAc=sodium acetate, ZnSt
2=Zinic stearas, ZnCO
3=zinc carbonate.
Claims (13)
1, a kind of modified epoxy resin composition that comprises following ingredients
(A) per molecule on average contains at least a Resins, epoxy that has 1 aromatic ring in epoxy group(ing) and its main chain at least more than 1; With
(B) by at least a polymkeric substance of one or more ethylenically unsaturated monomer preparations, wherein at least a this monomer contains the carboxylic acid group;
It is characterized in that in said composition, adding
(C) oxide compound, oxyhydroxide, carbonate or the organic carboxylate of I A, II A, II B, III A, VI B or VIII family metal at least a periodic table of elements.
2, a kind of solidification compound that comprises following component
(A) average per molecule contains more than one at least a Resins, epoxy that has an aromatic ring in epoxy group(ing) and its main chain at least;
(B) by at least a polymkeric substance of one or more ethylenically unsaturated monomer preparations, wherein at least a this monomer contains the carboxylic acid group; With
(D) solidifying agent of at least a component (A) of curing amount, this solidifying agent 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 said composition, adding
(C) at least a stabilizer compounds of stabilization amount, this compound are oxide compound, oxyhydroxide, carbonate or the organic carboxylate of periodic table of elements I A, II A, II B, III A, VI B or VIII family metal.
3, the solidification compound of claim 2, wherein catalyzer or promotor are added in the solidification compound in addition.
4, a kind of powder paint compositions that comprises following component
(A) average per molecule contains at least a Resins, epoxy that contains at least one aromatic ring more than one in abutting connection with epoxy group(ing) and in its main chain;
(B) at least a polymkeric substance that makes of one or more ethylenically unsaturated monomers, wherein at least a this monomer contains the carboxylic acid group;
(D) at least a solidifying agent that is different from the component (A) of component (B) or pre-reaction product (B) and (C); With
(E) at least a or multiple other component, this component comprises pigment, filler, flow control agent, levelling agent or other additive;
It is characterized in that in said composition, adding
(C) at least a stabilizer compounds of stabilization amount, this compound are oxide compound, oxyhydroxide, carbonate or the organic carboxylate of periodic table of elements I A, II A, II B, III A, VI B or VIII family metal.
5, each modified epoxy resin composition or solidification compound or powder paint compositions among the claim 1-4, wherein
(a) component (A) is the glycidyl ether of following composition; Dihydric phenol, bis-phenol, phenol or replace phenol-formaldehyde resin, phenol-or substituted phenol-unsaturated diene resin;
(b) component (B) is for being contained the polymkeric substance that ethene and aliphatic series, the monomer composition alicyclic or aromatic carboxylic acid produce by polymerization;
(c) component (C) is oxide compound, carbonate or the carboxylate salt of sodium, lithium, potassium, zinc, calcium, nickel, chromium or aluminium;
(d) component (D) is guanidine, biguanides, aliphatic amine, aromatic amine, the average per molecule compound, aliphatic series, cyclic aliphatic or the aromatics two that contain an above phenolic hydroxyl group-or polybasic acid anhydride, or the mixture of two or more these solidifying agent;
(e) consumption of component (A) is the 66-99%(weight of component (A) and gross weight (B));
(f) consumption of component (B) is the 1-34%(weight of component (A) and gross weight (B));
(g) consumption of component (C) should be enough to make the hydrogen atom of carboxyl contained in the component (B) of 4-100% to be replaced by the positively charged ion of periodic table of elements I A contained in the component (C), II A, II B, III A, VI B or VIII family element;
(h) consumption of component (D) should make this solidifying agent add that component (B) or its ionomeric equivalent and the ratio of the equivalent of epoxide are 0.8: 1-3: 1.
6, the modified epoxy resin composition of claim 5 or solidification compound or powder paint compositions, wherein
(a) component (A) is the glycidyl ether of ring phenol;
(b) polymkeric substance that produces for the monomer mixture that contains ethene and acrylic or methacrylic acid by polymerization of component (B);
(c) component (C) is the carbonate or the C of sodium, potassium, calcium or zinc
1-C
18Carboxylate salt, or be the mixture of two or more these stablizers;
(d) component (D) is that Dyhard RU 100, adjacent toluene guanyl guanidine, acid functional polyester, per molecule contain the compound of an above phenolic group, or be the mixture of two or more these class solidifying agent;
(e) component (A) consumption is the 80-96%(weight of component (A) and gross weight (B));
(f) consumption of component (B) is the 4-20%(weight of component (A) and gross weight (B));
(g) consumption of component (C) should be enough to make the positively charged ion of periodic table of elements I A, II A, II B, III A, VI B or VIII family element that the hydrogen atom of the carboxyl that contains in the 8-50% component (B) contained in the component (C) to replace;
(h) consumption of component (D) should make this solidifying agent add that component (B) or its ionomeric equivalent and the ratio of the equivalent of epoxide are 0.9: 1-2.5: 1.
7, the modified epoxy resin composition of claim 5 or solidification compound or powder paint compositions, wherein
(a) component (A) is the glycidyl ether of dihydroxyphenyl propane, Bisphenol F or bis-phenol K;
(b) component (B) is for being contained the polymkeric substance that ethene and acrylic acid monomer mixture produce by polymerization;
(c) component (C) is carbonate, acetate, propionic salt or the stearate of sodium, calcium or zinc, or its mixture;
(d) component (D) is the Dyhard RU 100 that Dyhard RU 100 or imidazoles quicken;
(e) consumption of component (A) is the 80-92%(weight of component (A) and gross weight (B));
(f) consumption of component (B) is the 8-20%(weight of component (A) and gross weight (B));
(g) consumption of component (C) should be enough to make the positively charged ion of periodic table of elements I A, II A, II B, III A, VI B or VIII family element that the hydrogen atom of the carboxyl that contains in the 8-20% component (B) contained by component (C) to replace;
(h) consumption of component (D) should make this solidifying agent add that component (B) or its ionomeric equivalent and the ratio of the equivalent of epoxide are 1: 1-2: 1.
8, the product that solidify to produce of claim 2,4,5 or 6 each solidification compounds.
9, the goods that apply of claim 3,4,5 or 6 powder paint compositions.
10, be suitable for use as the composition of epoxy curing agent, said composition comprises:
(1) at least a polymkeric substance that makes by one or more ethylenically unsaturated monomers, wherein at least a this monomer contains the carboxylic acid group; With
(2) at least a this curing agent for epoxy resin that is different from component (1); It is characterized in that in this curing agent composition, adding
(3) oxide compound, oxyhydroxide, carbonate or the organic carboxylate of at least a periodic table of elements I A, II A, II B, III A, VI B or the VIII family metal of stabilization amount.
11, the composition of claim 10, wherein
(a) amount of component (1) is the 1-99%(weight of the gross weight of component (1) and (2));
(b) amount of component (2) is the 99-1%(weight of the gross weight of component (1) and (2));
(c) amount of component (3) should be enough to make the contained hydrogen atom of carboxyl of 4-100% component (1) to be replaced by the positively charged ion of the contained periodic table of elements I A of component (3), II A, II B, III A, VI B or VIII family element.
12, the composition of claim 11 has wherein also used curing catalyst or catalyzer in addition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82778192A | 1992-01-29 | 1992-01-29 | |
| US07/827,781 | 1992-01-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1074919A true CN1074919A (en) | 1993-08-04 |
Family
ID=25250149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93100906A Withdrawn CN1074919A (en) | 1992-01-29 | 1993-01-28 | Modified epoxy resin composition, solidification compound and coatings with low gloss finish composition |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0624183A1 (en) |
| JP (1) | JPH07503279A (en) |
| KR (1) | KR950700374A (en) |
| CN (1) | CN1074919A (en) |
| AU (1) | AU3593893A (en) |
| BR (1) | BR9305888A (en) |
| CA (1) | CA2128414A1 (en) |
| MX (1) | MX9300478A (en) |
| NO (1) | NO942815L (en) |
| TW (1) | TW252124B (en) |
| WO (1) | WO1993015158A1 (en) |
| ZA (1) | ZA93616B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036206C (en) * | 1994-01-14 | 1997-10-22 | 希尔斯股份公司 | Process for the production of matt epoxy resin coatings |
| WO2010078688A1 (en) * | 2009-01-06 | 2010-07-15 | Dow Global Technologies Inc. | Metal stabilizers for epoxy resins |
| WO2010078690A1 (en) * | 2009-01-06 | 2010-07-15 | Dow Global Technologies Inc. | Metal stabilizers for epoxy resins and dispersion process |
| CN111032700A (en) * | 2017-09-05 | 2020-04-17 | 富士胶片株式会社 | Curable composition, cured product, and lens unit |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000006619A1 (en) | 1998-07-27 | 2000-02-10 | E.I. Du Pont De Nemours And Company | Mixed-metal-neutralized-copolymer-resins for metal coating powder applications |
| US6882058B2 (en) * | 2002-11-05 | 2005-04-19 | Henkel Corporation | Organic acid containing compositions and methods for use thereof |
| JP2006182963A (en) * | 2004-12-28 | 2006-07-13 | Honda Motor Co Ltd | Coating composition and automotive body-constituting member |
| DE102009031278B4 (en) | 2009-06-30 | 2017-10-05 | REMIS Gesellschaft für Entwicklung und Vertrieb von technischen Elementen mit beschränkter Haftung | Food freezer and cover for this |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL126705C (en) * | 1964-07-31 | Carnaud & Forges | ||
| US4419495A (en) * | 1981-09-21 | 1983-12-06 | The Dow Chemical Company | Epoxy resin powder coatings having low gloss |
-
1993
- 1993-01-27 EP EP93904648A patent/EP0624183A1/en not_active Withdrawn
- 1993-01-27 AU AU35938/93A patent/AU3593893A/en not_active Abandoned
- 1993-01-27 KR KR1019940702624A patent/KR950700374A/en not_active Application Discontinuation
- 1993-01-27 BR BR9305888A patent/BR9305888A/en not_active Application Discontinuation
- 1993-01-27 WO PCT/US1993/000702 patent/WO1993015158A1/en not_active Application Discontinuation
- 1993-01-27 JP JP5513394A patent/JPH07503279A/en active Pending
- 1993-01-27 CA CA002128414A patent/CA2128414A1/en not_active Abandoned
- 1993-01-28 ZA ZA93616A patent/ZA93616B/en unknown
- 1993-01-28 CN CN93100906A patent/CN1074919A/en not_active Withdrawn
- 1993-01-28 TW TW082100498A patent/TW252124B/zh active
- 1993-01-28 MX MX9300478A patent/MX9300478A/en unknown
-
1994
- 1994-07-28 NO NO942815A patent/NO942815L/en unknown
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036206C (en) * | 1994-01-14 | 1997-10-22 | 希尔斯股份公司 | Process for the production of matt epoxy resin coatings |
| WO2010078688A1 (en) * | 2009-01-06 | 2010-07-15 | Dow Global Technologies Inc. | Metal stabilizers for epoxy resins |
| WO2010078690A1 (en) * | 2009-01-06 | 2010-07-15 | Dow Global Technologies Inc. | Metal stabilizers for epoxy resins and dispersion process |
| 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 |
| CN102272252B (en) * | 2009-01-06 | 2014-05-28 | 陶氏环球技术有限责任公司 | Metal stabilizers for epoxy resins and dispersion process |
| CN111032700A (en) * | 2017-09-05 | 2020-04-17 | 富士胶片株式会社 | Curable composition, cured product, and lens unit |
| CN111032700B (en) * | 2017-09-05 | 2022-04-26 | 富士胶片株式会社 | Curable composition, cured product, and lens unit |
| US11603457B2 (en) | 2017-09-05 | 2023-03-14 | Fujifilm Corporation | Curable composition, cured product, and lens unit |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07503279A (en) | 1995-04-06 |
| NO942815L (en) | 1994-09-21 |
| NO942815D0 (en) | 1994-07-28 |
| AU3593893A (en) | 1993-09-01 |
| BR9305888A (en) | 1997-08-19 |
| CA2128414A1 (en) | 1993-08-05 |
| ZA93616B (en) | 1994-07-28 |
| WO1993015158A1 (en) | 1993-08-05 |
| MX9300478A (en) | 1993-07-01 |
| EP0624183A1 (en) | 1994-11-17 |
| TW252124B (en) | 1995-07-21 |
| KR950700374A (en) | 1995-01-16 |
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C03 | Withdrawal of patent application (patent law 1993) | ||
| WW01 | Invention patent application withdrawn after publication |