CN107418351B - A kind of one-component water solubility release-free electrochemical aluminum paint and preparation method thereof - Google Patents
A kind of one-component water solubility release-free electrochemical aluminum paint and preparation method thereof Download PDFInfo
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/48—Acrylonitrile with nitrogen-containing monomers
-
- 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
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/18—Homopolymers or copolymers of nitriles
- C09D133/20—Homopolymers or copolymers of acrylonitrile
Abstract
The present invention relates to technical field of paint preparation, in particular to a kind of electrochemical aluminum paint and preparation method thereof.A kind of one-component water solubility release-free electrochemical aluminum paint of the invention, including one-component water-soluble resin, deionized water, cosolvent and aqueous defoamer, the one-component water-soluble resin is prepared by reaction in parts by weight, by following component: first kind monomer, the second class monomer, third class monomer, N hydroxymethyl acrylamide, initiator, organic solvent, neutralizer.Phenomena such as major ingredient of electrochemical aluminum paint of the present invention is water-soluble resin, and compared with common water milk type coating, since emulsifier-free adds, emulsifier residue problem is not present, and storage time is long, no precipitating.The water-soluble resin is one-component self-cross linking type, and compared with common two-component resin, operating procedure is simple, and performance is stablized, and can achieve quick-setting requirement.
Description
Technical field
The present invention relates to technical field of paint preparation, in particular to a kind of electrochemical aluminum paint and preparation method thereof.
Background technique
With the raising of social progress and people's quality of life, to the envelope of the packaging of commodity, the coating of fabric and books
The printings such as face are put forward higher requirements, and both having required surface to have certain spectral color again has metal color.Electrochemical aluminum foil can generation
For metal foil as ornament materials, be with gold and silver color it is more, it has magnificent beauty, lovely luster, sparkling and crystal-clear brilliant, easy to use
The features such as, suitable for carrying out thermoprint in paper, textile, plastics, leather, coating fabric, organic glass, plastic or other material, it is
A kind of modern most common material of thermoprint binding and layout, demand are huge.
If existing anodized aluminium is the thermoprint material for forming dry coating by certain coating process on polyester film.Electricity
Change aluminium paint develops in recent years to be getting faster, and aqueous electrochemical aluminum paint is as energy saving and environment friendly electrochemical aluminum paint, also increasingly
Attention by researcher and product developer.Currently, aqueous electrochemical aluminum paint is divided into water-soluble, water-dispersion type and emulsion type
Three classes.There is post-processings to bother for common water milk type coating, at high cost, emulsifier residual, it is difficult to the problems such as removing, certain journey
The performance of product is influenced on degree；Meanwhile water milk type coating storage time is short, is easy to appear demulsification, generates precipitating.Common is water-soluble
Property coating typically belong to two-component resin, operating procedure is complicated, and stability is more difficult to control, and curing time is longer.
There is also the problems of temperature tolerance difference for existing electrochemical aluminum paint, and since temperature tolerance is poor, heatproof section is narrow, work as anodized aluminium
The molding temperature of coating makes processing parameter index undesirable after exceeding the temperature range, causes film performance cannot
Enough meet next procedure requirement, is easy to produce the phenomenon that peeling glues version, how to solve temperature range narrow range to technological parameter
It influences, that is, it is scarce present in existing production technology to solve to provide a kind of biggish electrochemical aluminum paint composition of adaptive temperature range
It falls into, is problem in the urgent need to address.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of high temperature resistant, solvent resistant, quick-drying one-component
Water-soluble release-free electrochemical aluminum paint, including one-component water-soluble resin, deionized water, cosolvent and aqueous defoamer, it is described
One-component water-soluble resin is prepared by reaction in parts by weight, by following component:
Wherein, the first kind monomer is one or more of methyl methacrylate, styrene, acrylonitrile；
The second class monomer is one or more of butyl acrylate, ethyl acrylate, isobutyl acrylate；
The third class monomer is one or both of methacrylic acid, acrylic acid.
The organic solvent is one or more of acetone, butanone, ethyl alcohol, n-butanol, isopropanol.
The neutralizer is one or more of triethylamine, dimethylethanolamine, ammonium hydroxide.
The initiator is one or both of dibenzoyl peroxide, azodiisobutyronitrile.
It is a further object of the present invention to provide a kind of preparation method of above-mentioned one-component water solubility release-free electrochemical aluminum paint,
Include the following steps:
1, one-component water-soluble resin is prepared
It is passed through nitrogen 3-8min into reaction vessels, removes the oxygen in reactor；After ventilation be added organic solvent,
N hydroxymethyl acrylamide, the initiator of initiator total amount 30% and one third by first kind monomer, the second class monomer and
The mix monomer of third class monomer composition starts to carry out pre-reaction 30-60min at 75 DEG C；Reaction temperature is increased to 80-83
DEG C, when mixed system temperature reaches 80-83 DEG C of set temperature in reaction utensil, start that remaining mix monomer and initiator is added dropwise
The initiator of total amount 60%, control rate of addition drip off residual monomer in 3.5-4h, initiator are added after the reaction was continued 1h
The initiator of total amount 10%, then carries out insulation reaction, soaking time 3-3.5h, be added after completion of the reaction neutralizer to resin into
Row neutralizes, after mixing evenly cooling discharging；
2, electrochemical aluminum paint is prepared
A certain amount of one-component water-soluble resin is weighed, solid content addition cosolvent and deionized water tune as required
The weight ratio of examination resin, cosolvent and deionized water is 1:1；It is added with the aqueous of one-component water-soluble resin meter 0.25%
Defoaming agent stirs evenly, and coating can also be carried out by standing 5-10min.
The cosolvent is one or two kinds of in isopropanol or ethyl alcohol.
Electrochemical aluminum paint of the invention is added to N hydroxymethyl acrylamide as self-crosslinking in the synthesis process of resin
Agent, since the solubility of N hydroxymethyl acrylamide in organic solvent is smaller, thus it is pre- using first dissolution in low temperature in synthesis process
Reaction, the method for then carrying out temperature reaction realize this compound purpose evenly dispersed in resin.
The major ingredient of electrochemical aluminum paint of the present invention is water-soluble resin, compared with common water milk type coating, due to no emulsification
Phenomena such as agent addition, is not present emulsifier residue problem, and storage time is long, no precipitating.The water-soluble resin is one-component selfing
Connection type, compared with common two-component resin, operating procedure is simple, and performance is stablized, and can achieve quick-setting requirement.Simultaneously
Electrochemical aluminum paint of the invention, by the performance of adjusting resin, achievees the purpose that release-free without adding mould release, can be effective
Save the cost reduce pollution.The present invention also solves the disadvantage that aqueous electrochemical aluminum paint poor solvent resistance to a certain extent,
As a kind of coating application simple process of self-cross linking type, mistake and loss, belong to caused by largely reducing because of construction
In a kind of environment-friendly type electrochemical aluminum paint.
Specific embodiment
Embodiment 1
A kind of one-component water solubility release-free electrochemical aluminum paint, including one-component water-soluble resin, deionized water, cosolvent
And aqueous defoamer, the one-component water-soluble resin in parts by weight, by following component:
120 parts of methyl methacrylate
23 parts of butyl acrylate
22 parts of methacrylic acid
5 parts of N hydroxymethyl acrylamide
2 parts of dibenzoyl peroxide
150 parts of acetone
6 parts of triethylamine
It is prepared by the following method:
1, one-component water-soluble resin is prepared
It is passed through nitrogen 3-8min into reaction vessels, removes the oxygen in reactor；Acetone, N- hydroxyl are added after ventilation
Methacrylamide, 30% dibenzoyl peroxide and one third by methyl methacrylate, butyl acrylate and first
The mix monomer of base acrylic acid composition starts to carry out pre-reaction 30-60min at 75 DEG C；Reaction temperature is increased to 80-83 DEG C,
When mixed system temperature reaches 80-83 DEG C of set temperature in reaction utensil, start the mistake that remaining mix monomer and 60% is added dropwise
Dibenzoyl is aoxidized, control rate of addition drips off residual monomer in 3.5-4h, and 10% peroxide is added after the reaction was continued 1h
Change dibenzoyl, then carry out insulation reaction, triethylamine is added in resin progress in soaking time 3-3.5h after completion of the reaction
With cooling discharging after mixing evenly.
2, electrochemical aluminum paint is prepared
A certain amount of one-component water-soluble resin is weighed, adds isopropanol and deionized water tune according to 20% solid content
The weight ratio of examination resin, isopropanol and deionized water is 1:1；It is added with the aqueous of one-component water-soluble resin meter 0.25%
Defoaming agent stirs evenly, and coating can also be carried out by standing 5-10min.
Embodiment 2
A kind of one-component water solubility release-free electrochemical aluminum paint, including one-component water-soluble resin, deionized water, cosolvent
And aqueous defoamer, the one-component water-soluble resin in parts by weight, by following component:
115 parts of styrene
23 parts of ethyl acrylate
25 parts of acrylic acid
5 parts of N hydroxymethyl acrylamide
2 parts of azodiisobutyronitrile
150 parts of ethyl alcohol
6 parts of dimethylethanolamine
It is prepared by the following method:
1, one-component water-soluble resin is prepared
It is passed through nitrogen 3-8min into reaction vessels, removes the oxygen in reactor；Ethyl alcohol, N- hydroxyl are added after ventilation
Methacrylamide, 30% azodiisobutyronitrile and one third be made of styrene, ethyl acrylate and acrylic acid
Mix monomer starts to carry out pre-reaction 30-60min at 75 DEG C；Reaction temperature is increased to 80-83 DEG C, to mix in reaction utensil
When system temperature reaches 80-83 DEG C of set temperature, start the azodiisobutyronitrile that remaining mix monomer and 60% is added dropwise, controls
Rate of addition drips off residual monomer in 3.5-4h, and 10% azodiisobutyronitrile is added after the reaction was continued 1h, then carries out
Dimethylethanolamine is added after completion of the reaction and neutralizes to resin by insulation reaction, soaking time 3-3.5h, cold after mixing evenly
But it discharges.
2, electrochemical aluminum paint is prepared
A certain amount of one-component water-soluble resin is weighed, adds isopropanol and deionized water tune according to 20% solid content
The weight ratio of examination resin, ethyl alcohol and deionized water is 1:1；Addition is disappeared with the aqueous of one-component water-soluble resin meter 0.25%
Infusion stirs evenly, and coating can also be carried out by standing 5-10min.
Embodiment 3
A kind of one-component water solubility release-free electrochemical aluminum paint, including one-component water-soluble resin, deionized water, cosolvent
And aqueous defoamer, the one-component water-soluble resin in parts by weight, by following component:
110 parts of acrylonitrile
25 parts of isobutyl acrylate
20 parts of methacrylic acid
5 parts of N hydroxymethyl acrylamide
2 parts of dibenzoyl peroxide
150 parts of isopropanol
6 parts of ammonium hydroxide
It is prepared by the following method:
1, one-component water-soluble resin is prepared
It is passed through nitrogen 3-8min into reaction vessels, removes the oxygen in reactor；Isopropanol, N- are added after ventilation
Hydroxymethyl acrylamide, 30% dibenzoyl peroxide and one third by acrylonitrile, isobutyl acrylate and methyl-prop
The mix monomer of olefin(e) acid composition starts to carry out pre-reaction 30-60min at 75 DEG C；Reaction temperature is increased to 80-83 DEG C, to anti-
When answering that mixed system temperature reaches 80-83 DEG C of set temperature in ware, start the peroxidating that remaining mix monomer and 60% is added dropwise
Dibenzoyl, control rate of addition drip off residual monomer in 3.5-4h, and 10% peroxidating two is added after the reaction was continued 1h
Benzoyl, then carries out insulation reaction, and ammonium hydroxide is added after completion of the reaction and neutralizes to resin, stirs by soaking time 3-3.5h
Cooling discharging after uniformly.2, electrochemical aluminum paint is prepared
A certain amount of one-component water-soluble resin is weighed, isopropanol is added by 20% solid content and deionized water is debugged
The weight ratio of resin, isopropanol and deionized water is 1:1；Addition is disappeared with the aqueous of one-component water-soluble resin meter 0.25%
Infusion stirs evenly, and coating can also be carried out by standing 5-10min.
Contrast test example
Testing standard: resistance to butanone solvent test after dipping butanone with cotton swab, wipes 10 times, not show-through for qualification.Heatproof is surveyed
Examination: at a certain temperature, using pressing machine pressing certain temperature, membrane stage of aluminizing is observed, if discoloration illusion-colour occur, such as occur
This state is considered as unqualified.
Comparative example is commercially available two-component electrochemical aluminum paint (the thermal transfer coating of Wan Jia thermal transfer factory production)
。
Claims (5)
1. a kind of one-component water solubility release-free electrochemical aluminum paint, it is characterised in that: including one-component water-soluble resin, deionization
Water, cosolvent and aqueous defoamer, the one-component water-soluble resin pass through reaction preparation in parts by weight, by following component
It obtains:
110-120 parts of first kind monomer
Second 20-30 parts of class monomer
16-25 parts of third class monomer
3-6 parts of N hydroxymethyl acrylamide
1.5-3 parts of initiator
145-160 parts of organic solvent
5-8 parts of neutralizer
The first kind monomer is one or more of methyl methacrylate, styrene, acrylonitrile；
The second class monomer is one or more of butyl acrylate, ethyl acrylate, isobutyl acrylate；
The third class monomer is one or both of methacrylic acid, acrylic acid；
Specifically comprise the following steps:
(1) one-component water-soluble resin is prepared
It is passed through nitrogen 3-8min into reactor, removes the oxygen in reactor；Organic solvent, N- hydroxyl first are added after ventilation
Base acrylamide, the initiator of initiator total amount 30% and one third by first kind monomer, the second class monomer and third class list
The mix monomer of body composition starts to carry out pre-reaction 30-60min at 75 DEG C；Reaction temperature is increased to 80-83 DEG C, wait react
When mixed system temperature reaches 80-83 DEG C of set temperature in device, start to be added dropwise remaining mix monomer and initiator total amount 60%
Initiator, control rate of addition drip off residual monomer in 3.5-4h, drawing for initiator total amount 10% are added after the reaction was continued 1h
Agent is sent out, insulation reaction is then carried out, neutralizer is added after completion of the reaction and neutralizes to resin, stirs by soaking time 3-3.5h
Cooling discharging after uniformly；
(2) electrochemical aluminum paint is prepared
A certain amount of one-component water-soluble resin is weighed, solid content addition cosolvent and deionized water debugging tree as required
The weight ratio of rouge, cosolvent and deionized water is 1:1；It is added with the aqueous defoaming of one-component water-soluble resin meter 0.25%
Agent stirs evenly, and stands 5-10min and carries out coating.
2. a kind of one-component water solubility release-free electrochemical aluminum paint according to claim 1, it is characterised in that: the initiation
Agent is one or both of dibenzoyl peroxide, azodiisobutyronitrile.
3. a kind of one-component water solubility release-free electrochemical aluminum paint according to claim 1, it is characterised in that: described organic
Solvent is one or more of acetone, butanone, ethyl alcohol, n-butanol, isopropanol.
4. a kind of one-component water solubility release-free electrochemical aluminum paint according to claim 1, it is characterised in that: the neutralization
Agent is one or more of triethylamine, dimethylethanolamine, ammonium hydroxide.
5. a kind of one-component water solubility release-free electrochemical aluminum paint according to claim 1, it is characterised in that: step (2)
Described in cosolvent be one or two kinds of in isopropanol or ethyl alcohol.
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| CN201710651670.3A CN107418351B (en) | 2017-08-02 | 2017-08-02 | A kind of one-component water solubility release-free electrochemical aluminum paint and preparation method thereof |
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| CN108893024A (en) * | 2018-06-01 | 2018-11-27 | 浙江枧洋高分子科技有限公司 | A kind of low-temperature fast-curing electrochemical aluminum paint |
| CN109651559B (en) * | 2018-12-11 | 2021-11-09 | 上海绘兰材料科技有限公司 | Acrylic resin for release-free ironing cloth electrochemical aluminum and preparation method and application thereof |
| CN114262564A (en) * | 2022-01-20 | 2022-04-01 | 广东瑞通新材料科技有限公司 | Release-free water-based alumite coating and preparation method thereof |
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| CN103396508A (en) * | 2013-07-29 | 2013-11-20 | 华南理工大学 | Low-temperature self-crosslinked water-based acrylate resin, and preparation method and application thereof |
| CN105038555A (en) * | 2015-08-04 | 2015-11-11 | 上海乘鹰新材料有限公司 | Water-based laser alumite coating without release layer and preparation method thereof |
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| CN102585645B (en) * | 2012-03-05 | 2014-05-28 | 湖北联合天诚防伪技术股份有限公司 | Anti-counterfeiting electrolytic aluminum coating and preparation method thereof |
| JP2016155923A (en) * | 2015-02-24 | 2016-09-01 | 関西ペイント株式会社 | Hydrophilic paint composition and heat exchanger aluminum fin material |
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| CN103396508A (en) * | 2013-07-29 | 2013-11-20 | 华南理工大学 | Low-temperature self-crosslinked water-based acrylate resin, and preparation method and application thereof |
| CN105038555A (en) * | 2015-08-04 | 2015-11-11 | 上海乘鹰新材料有限公司 | Water-based laser alumite coating without release layer and preparation method thereof |
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