Water-based paint compositions
Technical field
The present invention relates to paint field, particularly relate to the decorative paint for rostone artwork, ceramic artwork, plastics, particularly relate to a kind ofly to brush, spray, water-based industrial art coating that dip-coating and printing use.
Background technology
Nitro paint is the kind that a class consumption is larger.Containing the petroleum solvent of 45 ~ 55% weight parts of having an appointment in this kind of system component thing, petroleum solvent used is complicated mixture, wherein containing more multiring aromatic hydrocarbon substance, comprises the carcinogenic composition that some are strong, as: 3,4-benzo pyrrole, 3-nitro benzo ketone etc.Use artwork, ceramic artwork or plastics etc. that this coatings decoration is made with unsaturated polyester resin and stone flour stopping composition, objectionable impurities residual quantity on artwork can be made large, the survival time is long, chronic hazard will be caused to user is healthy, also be the environomental pollution source of coating material production and use procedure, caused people greatly to pay close attention to.
This not only environmental protection of use industrial art coating but also the resource that can regenerate replace non-renewable petroleum solvent, rise in current oil price, under situation that resource constantly reduces, excite enthusiasm and confidence that domestic and international professional person researches and develops water-based industrial art coating.This is a behave promoting human environment close friend and save energy, has very large reality and far-reaching significance.But how to make take water as the coating of primary solvent, can rapid drying, sticking power large, brush, spraying, dip-coating and printing performance good, become the key of problem.CN1415673A, CN1410495A, CN0310748A, CN1239123A, CN1079488A, CN14720282A etc. never ipsilateral disclose the autonomous innovation scheme that contriver provides with regard to the problems referred to above.Even so, this area is reflected in a series of technical measures such as such as low-melting ink vehicle, auxiliary agent, rate of drying, sticking power, water tolerance also also exist and updates and perfect space in formulation for coating material, manufacturing process.
Summary of the invention
The present invention proposes a kind of new environment-friendly type technique artistic coating formula, to improve the security of coating system, covering with paint property, drying property, consistency and stability.
According to water-based paint compositions of the present invention, comprise: high acid value acrylic resin amination liquid (A), it is the water soluble resin liquid made through amination reaction with high acid value acrylic resin, described high acid value refers to the scope of 140 ~ 280mgKOH/g, the preferably scope of 180 ~ 260mgKOH/g, more preferably the scope of 200 ~ 240mgKOH/g, the most preferably scope of 215 ~ 225mgKOH/g; AA emulsion, as membrane-forming agent; Pure water, as solvent; And alcohol or alcohol ether solubility promoter.
In a preferred embodiment, carrying out amination reaction aminating agent used is ammoniacal liquor and Monoethanolamine MEA BASF, and the pH value of described amination liquid is 8.5 ~ 9.5.
In a preferred embodiment, for the preparation of the molecular weight of the acrylic resin of described amination liquid between 5000-12000, preferably 7000 ~ 9500 scope.
In a preferred embodiment, described AA emulsion comprises: the latex of copolymer in cinnamic acrylic ester (B) of low Tg value, described low Tg value refers to that second-order transition temperature is no more than 10 DEG C, preferably more than 0 DEG C, more preferably no more than-5 DEG C, be most preferably not exceeding-8 DEG C, the molecular weight of styrene-acrylic resins is in the scope of 50000-100000; And the latex of copolymer in cinnamic acrylic ester of high tg values (C), described high tg values refers to that second-order transition temperature is not less than 60 DEG C, preferably be not less than 80 DEG C, be more preferably not less than 90 DEG C, in emulsion, the molecular weight of styrene-acrylic resins is in the scope of 100000-200000.
Aforementioned coating composition is alternatively containing one or more in adhesion promoter, static inhibitor, surface slip agent, stablizer, thickening material, defoamer, perfuming agent.
Water-based industrial art coating manufactured according to the present invention, has safety and environmental protection feature, fast, the resistance to wet friction of rate of drying, sticking power is high, be coated with that (print) brush adaptive is good, gloss greatly, the feature such as cost is lower.
Embodiment
One of key character of the present invention is in coating system, introduce high acid value acrylic resin amination liquid.The present invention's high acid value acrylic resin amination liquid used carries out amination with the acrylic resin of high acid value and obtains.Here high acid value refers to the acid value of 140 ~ 280mgKOH/g.The scope of the preferred 180 ~ 260mgKOH/g of the present invention, the more preferably scope of 200 ~ 240mgKOH/g, the most preferably scope of 215 ~ 225mgKOH/g, poorly water-soluble after the too low then resin amination of acid number; If acid number is too high, then poor water resistance after coating film forming.The molecular-weight average of acrylic resin is suitable between 5000-12000, and molecular weight is too low, then resin amination fluid viscosity is too low, can produce dry epithelium and after-tack; Too high then resin amination fluid viscosity is too high, is unfavorable for that dispersible pigment color paste disperses.Wherein preferred 7000 ~ 9500 scope.Softening temperature is preferably between 140 ~ 160 DEG C.High acid value acrylic resin can introduce the present invention with the form of solid-state, semi-solid state (i.e. paste) or liquid state, and its liquid solid content can between 30 ﹪ ~ 50 ﹪.
Aminating agent for amination acrylic resin can be selected from ammoniacal liquor, Monoethanolamine MEA BASF, diethanolamine, 2-amino-2-methyl-1-propanol etc., the present invention preferably adopts ammoniacal liquor and Monoethanolamine MEA BASF as varies agent, namely adopt ammoniacal liquor that the pH value of acrylic resin is adjusted to about about 7, then with Monoethanolamine MEA BASF, pH value is adjusted to the scope of 8.0 ~ 9.5.Adopt Monoethanolamine MEA BASF amination liquid can be made not have peculiar smell on the one hand, on the other hand, hydroxyl wherein, as hydrophilic radical, improves resin to the affinity of water, thus improves the stability in aqueous phase; Amino then the affinity improved pigment, thus it is dispersed in system to improve pigment, reaches and homogenizes.
Some other compositions are preferably added, such as solubility promoter, sanitas, stablizer etc. in amination liquid.Operable solubility promoter includes but not limited to ethylene glycol ethyl ether, Virahol, ethanol, n-propyl alcohol etc., operable stablizer include but not limited to urea, monoethanolamine, morpholine etc., operable sanitas includes but not limited to Sodium Benzoate, preferred food product level Sodium Benzoate of the present invention.
The acrylic resin amination liquid that the present invention introduces is the outstanding dispersion medium of pigment dyestuff and mineral dye, and with following filmogen, especially Styrene And Chloroalkyl Acrylates emulsion polymerization has excellent consistency.
In order to prepare acrylic resin amination liquid, selected acrylic resin slowly can be added in containing aminating agent with in the aqueous solution of other auxiliary agents, and then regulate PH to required scope with aminating agent.In a kind of embodiment, this working method comprises the following steps:
1. add water, ethylene glycol ethyl ether, Virahol (or ethanol), ammoniacal liquor in a kettle., under stirring, slowly add high acid value acrylic resin, extremely without particulate matter;
2. drip Monoethanolamine MEA BASF, transparent to solution, test pH value should be 8.5 ~ 9.5;
3. continue stirring 20 ~ 30 minutes, constantly test pH value, till pH value is constant;
4. in advance by pure water (2) dissolved urea and Sodium Benzoate, then add in acrylic resin amination liquid and stir, filter discharging with 120 eye mesh screens.
The solid content of the high acid value acrylic resin used in embodiments of the invention more than 95%, softening temperature (ring and ball method) 155 DEG C.
In the preferred embodiment of the present invention, using the styrene acrylic polymer emulsion of low Tg value as membrane-forming agent, using the styrene acrylic polymer emulsion of high tg values as secondary film formers, described low Tg value refers to that second-order transition temperature is no more than 10 DEG C.Preferably more than 0 DEG C in the present invention, more preferably no more than-5 DEG C, be most preferably not exceeding-8 DEG C, such as-10 DEG C.Wherein the molecular-weight average of styrene-acrylic resins is suitable in 50000-100000 scope, preferably the scope of 60000 ~ 100000, and more preferably 80000 ~ 90000.For the ease of processing, the solid content of emulsion preferably more than 40%, such as 48%.This emulsion directly can be obtained by letex polymerization, also can add appropriate solvent and the acquisition of the ancillary component such as emulsifying agent, stablizer after polymerization obtains polymkeric substance.Select aforementioned membrane-forming agent, water tolerance, oil-proofness and snappiness that excellent film-forming properties also can increase film can be provided, and the tack to nonporous substrate.
Described high tg values refers to that second-order transition temperature is not less than 60 DEG C.Preferably be not less than 80 DEG C in the present invention, be more preferably not less than 90 DEG C, such as 95 DEG C.Wherein the suitable molecular weight of styrene-acrylic resins is in the scope of 100000-200000, preferably 120000 ~ 180000 scope, more preferably 130000 ~ 150000.For the ease of processing, the solid content of emulsion preferably more than 40%, such as 48%, but other solid content also can use.This emulsion directly can be obtained by letex polymerization, also can add appropriate solvent and the acquisition of the ancillary component such as emulsifying agent, stablizer after polymerization obtains polymkeric substance.Select aforementioned secondary film formers, the hardness of film, gloss, thermotolerance accelerate the drying of film can be increased.
Above-mentioned styrene acrylic polymer emulsion is easy to obtain from market.
Previous embodiment is another feature of the present invention, namely, the styrene acrylic polymer emulsion above-mentioned two kinds with different Tg value with the use of, the dried forms of coating be based on volatile dry, to ooze solidifying drying be auxiliary combination drying form, thus make the rate of drying of coating increase than single dried forms, and the crocking resistance of film be there has also been significantly improve.Certainly, this is only a kind of preferred implementation of the present invention, aforesaid propylene acid resin amination liquid can also with the film-forming resin of other types with the use of, the example of these resins has high molecular weight water-soluble acrylic resin, aqueous epoxy resins, waterborne polyurethane resin, aqueous polyamide resin, aqueous cellulose resin, aqueous polyester resin etc.These resins are also emulsion or water soluble resin form usually, and the resin complex preferably with two kinds of second-order transition temperatures uses, respectively as main membrane-forming agent and secondary film formers.
Coating composition of the present invention take water as solvent, except above-mentioned main component, also comprises appropriate solubility promoter and functional aid.The example of operable solubility promoter includes but not limited to alcohols, wherein preferred alcohol.Conventional functional aid comprises adhesion promoter, static inhibitor, surface slip agent, stablizer, thickening material, defoamer, perfuming agent etc., and these are known by prior art.
Coating composition of the present invention can be prepared into colo(u)r coating, whitewash and varnish, and wherein varnish may be used for the coating oil of artwork and paper.Different application can adjust the content of mentioned component.
In order to prepare colo(u)r coating, need in system, introduce organic or inorganic pigment, or the combination of the two.Due to the effect of aforesaid propylene acid resin amination liquid, pigment can stably be dispersed in resin system, good film-forming property, and the film tool formed has good wearability and shock resistance.
Preparing the occasion of colo(u)r coating, the weight ratio of high acid value acrylic resin amination liquid (A), Styrene And Chloroalkyl Acrylates emulsion polymerization (B) and Styrene And Chloroalkyl Acrylates emulsion polymerization (C) is preferably about A:B:C=1:1:0.2, wherein uses relatively large amination liquid (A).Preparing the occasion of whitewash, preferred about A:B:C=2:3:0.7.Preparing the occasion of coating oil, owing to not comprising pigment, amination liquid (A) can use on a small quantity, about preferred A:B:C=1:10 ~ 12:2.5 ~ 3.5.The ratio of components (with parts by weight) that the specific embodiment below listing three kinds of typically used adopts:
Material name coating forms
Colo(u)r coating whitewash coating oil
High acid value acrylic resin amination liquid (A) 34.5 ~ 35.518.0 ~ 22.04.0 ~ 5.0
Styrene And Chloroalkyl Acrylates emulsion polymerization (B) 30.0 ~ 31.028.0 ~ 30.056.0 ~ 58.0
Styrene And Chloroalkyl Acrylates emulsion polymerization (C) 7.0 ~ 8.07.0 ~ 8.014.0 ~ 15.0
Pigment dyestuff 13.2 ~ 14.3
Rutile type Titanium Dioxide 28.0 ~ 30.0
Anatase thpe white powder 1.0 ~ 1.2
Inorganic fillings 0 ~ 0.5
Pure water 2.0 ~ 5.02.0 ~ 5.07.0 ~ 8.0
Co-solvent 5.0 ~ 5.56.0 ~ 8.06.0 ~ 7.0
Functional aid 7.3 ~ 7.86.0 ~ 7.09.0 ~ 10.0
In above-described embodiment, high acid value acrylic resin, its softening temperature (ring and ball method) 155 DEG C, acid number 215 ~ 225mgKOH/g, solids content >=97 ﹪, molecular weight 7000 ~ 9500.Styrene And Chloroalkyl Acrylates emulsion polymerization (B), its second-order transition temperature (Tg value)-10 DEG C, solids content 48 ﹪.Styrene And Chloroalkyl Acrylates emulsion polymerization (C), its second-order transition temperature (Tg value) 95 DEG C, solids content 48 ﹪.
embodiment 1: the preparation of high acid value acrylic resin amination liquid (A)
Material name |
Ratio of components |
High acid value acrylic resin |
20.0 |
Pure water (1) |
32.0 |
Ethylene glycol ethyl ether |
2.0 |
Virahol |
6.0 |
Ammoniacal liquor (content 25 ~ 28 ﹪) |
2.6 |
Monoethanolamine MEA BASF |
3.5 |
Pure water (2) |
30.5 |
Urea |
2.0 |
Sodium Benzoate (food grade) |
1.2 |
Froth breaking suds suppressor |
0.2 |
Add up to |
100.0 |
Operation steps:
Step 1: add pure water (1), ethylene glycol ethyl ether, Virahol, ammoniacal liquor in a kettle., slowly add high acid value acrylic resin under stirring, extremely without particulate matter.
Step 2: drip Monoethanolamine MEA BASF, transparent to solution.Test pH value, should be 8.5 ~ 9.5 (regulating with Monoethanolamine MEA BASF).
Step 3: continue stirring 20 ~ 30 minutes, constantly test pH value, till pH value is constant.
Step 4: in advance by pure water (2) dissolved urea and Sodium Benzoate, then add in acrylic resin amination liquid and stir, filters discharging with 120 eye mesh screens.
Technical indicator:
Be coated with-4# cup viscosity 15 ~ 25 seconds/25 ﹪; PH value 8.0 ~ 9.0
Appearance colorless transparent liquid.
embodiment 2: prepared by water-based coating oil
Raw material:
Material name |
Ratio of components |
High acid value acrylic resin amination liquid (A) |
5.0 |
Styrene acrylic polymer emulsion (B) |
60.0 |
Styrene acrylic polymer emulsion (C) |
15.0 |
Industrial alcohol |
7.0 |
Pure water |
8.0 |
The static inhibitor aqueous solution (10 ﹪) |
1.0 |
Adhesion promoter |
1.0 |
Polythene wax emulsion (wax content 35 ﹪) |
3.0 |
Water-based thickener |
4.0 |
Ammoniacal liquor (content 25 ~ 28 ﹪) |
0.7 |
High efficiency water defoamer |
0.2-0.4 (considering) |
Add up to |
105.0 |
Operation:
In mixer, be weighed into high acid value acrylic resin amination liquid (A), ethanol, pure water, adhesion promoter, the static inhibitor aqueous solution, stir.Then add styrene acrylic polymer emulsion (B), styrene acrylic polymer emulsion (C) and polythene wax emulsion, add high efficiency water defoamer (can not add, in case " shrinkage cavity " phenomenon) in right amount according to foam situation.
Add water-based thickener and ammoniacal liquor under stirring, adjustment viscosity is to acceptability limit.Filtration discharging is packed.
Technical indicator:
Appearance milky white liquid; Be coated with-4# cup viscosity 30 ~ 50 seconds/25 DEG C; PH value 8.0 ~ 9.0; Solids content 38 ± 1 ﹪.
Embodiment 3: the preparation of whitewash
Raw material:
Material name |
Ratio of components |
High acid value acrylic resin amination liquid (A) |
40.0 |
Rutile type Titanium Dioxide |
60.7 |
Ethylene glycol ethyl ether |
4.0 |
Virahol |
4.0 |
Industrial alcohol |
8.0 |
Pure water |
5.0 |
The static inhibitor aqueous solution (10 ﹪) |
5.0 |
Adhesion promoter |
1.0 |
High efficiency water defoamer |
0.2-0.4 (considering) |
|
|
Styrene acrylic polymer emulsion (B) |
60.0 |
Styrene acrylic polymer emulsion (C) |
15.0 |
Polythene wax emulsion (wax content 35 ﹪) |
3.0 |
Water-based thickener |
4.3 |
Ammoniacal liquor (content 25 ~ 28 ﹪) |
0.7 |
Water-borne coatings perfuming agent |
0.02-0.1﹪ |
Add up to |
211.0 |
|
|
Working method:
Step 1: by each material taken successively in mixer except benzene emulsion and wax emulsion of filling a prescription, stir about 30 minutes first quick and back slow under being placed in homogenizer, carry out mixing pre-dispersed.
Step 2: pre-dispersed good slurry is moved to sand mill grinding.General grinding 3 ~ 4 times, often all over 1 ~ 1.5 hours.Until coating fineness reaches less than 15 microns.
Step 3: other indexs of sampling and testing, qualified or through adjust qualified after can pack.
Step 4: qualified coating is filtered to pail pack through 120 order copper wire gauze, covers tightly bung, post trade mark, can put in storage.
Technical indicator:
Whiteness and opacifying power similar to standard; Fineness≤15 micron; Be coated with-4# cup viscosity 40 ~ 60 seconds/25 DEG C; PH value 8.0 ~ 9.0; Surface drying (room temperature 25 ﹪ relative humidity 60 ~ 70 ﹪)≤3 minutes.
embodiment 4: the preparation of colo(u)r coating
Raw material: see table 1.
Table 1
Material name |
Bright red |
Pinkish red |
Middle Huang |
Sky blue |
Black |
Green |
High acid value acrylic resin amination liquid (A) |
34.5 |
35.5 |
35.5 |
34.5 |
35.0 |
35.0 |
Light-resistant scarlet BBN |
12.0 |
|
|
|
|
|
Fuchsin 6B-350SD |
|
11.2 |
|
|
|
|
Lithol Red R |
2.2 |
2.0 |
|
|
|
|
Diarylide yellow (PY.12) |
|
|
13.2 |
|
|
|
Phthalocyanine Blue BGS |
|
|
|
14.0 |
|
|
Roller black |
|
|
|
|
9.5 |
|
N-330 carbon black |
|
|
|
|
4.1 |
|
Phthalocyanine blue b |
|
|
|
|
0.7 |
|
Phthalocyanine Green G |
|
|
|
|
|
13.5 |
Titanium dioxide BA01-01 |
1.0 |
1.0 |
1.2 |
1.2 |
|
1.2 |
Light calcium carbonate |
|
|
|
0.3 |
|
0.5 |
Ethylene glycol ethyl ether |
2.0 |
2.0 |
2.0 |
2.0 |
2.0 |
2.0 |
Virahol |
2.0 |
2.0 |
2.0 |
2.0 |
2.0 |
2.0 |
Ethanol |
1.5 |
1.0 |
1.2 |
1.5 |
1.5 |
1.2 |
Pure water |
2.0 |
2.0 |
2.0 |
2.0 |
2.0 |
2.0 |
Static inhibitor (the 10 ﹪ aqueous solution) |
2.5 |
3.0 |
2.5 |
2.5 |
2.5 |
2.5 |
Adhesion promoter |
0.3 |
0.3 |
0.3 |
0.3 |
0.3 |
0.3 |
High efficiency water defoamer |
0.3 |
0.3 |
0.3 |
0.3 |
0.4 |
0.3 |
Styrene acrylic polymer emulsion (B) |
30.0 |
30.0 |
30.0 |
30.0 |
31.0 |
30.0 |
Styrene acrylic polymer emulsion (C) |
8.0 |
8.0 |
8.0 |
8.0 |
7.0 |
8.0 |
Polythene wax emulsion |
3.0 |
3.0 |
3.0 |
3.0 |
3.0 |
3.0 |
Water-based thickener |
2.5 |
2.0 |
2.5 |
2.5 |
1.0 |
2.5 |
Ammoniacal liquor (25-28 ﹪) |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
Water-borne coatings perfuming agent |
0.01 |
0.01 |
0.01 |
0.01 |
0.01 |
0.01 |
M-tetrachlorophthalodinitrile (the 1 ﹪ aqueous solution) |
0.4 |
0.4 |
0.4 |
0.4 |
0.4 |
0.4 |
Add up to |
104.3 |
103.8 |
104.2 |
104.6 |
102.5 |
104.5 |
Operation:
Step 1: by each material taken successively in mixer except benzene emulsion and wax emulsion of filling a prescription, stir about 30 minutes first quick and back slow under being placed in homogenizer, carry out mixing pre-dispersed.
Step 2: pre-dispersed good slurry is moved to sand mill grinding.General grinding 4-5 compiles, often all over 1 ~ 1.5 hours; Black grinds 6 times or more, often all over 1 ~ 1.5 hours.Until coating fineness reaches less than 15 microns.
Technical indicator:
It is similar to standard that color scrapes sample; Tinting strength is 95 ~ 110 ﹪ of standard;
Fineness≤15 micron; Be coated with-4# cup viscosity 40 ~ 60 seconds/25 DEG C;
Seconds 25 DEG C, first dryness 10 ~ 30 millimeters/30;
Sticking power (after 24 hours) scotch tape is sticky to be drawn without coming off;
Rub-off resistance (after 24 hours) is rubbed 20 nothings and is come off and jackknifing trace;
Water tolerance (after 24 hours) is soaked in the neutral water 24 hours not loss of gloss that do not fade.
Water-based industrial art coating made by the present invention, take full advantage of the water resources of cheapness, sanitation and hygiene, the harm decreasing environmental pollution and bring HUMAN HEALTH, the nuisance that the characteristic of environmental protection of itself and handicraft surface remain can reach safety and sanitation standard, is extensively admitted.This water-based industrial art coating, except can adapting to the feature of brushing, spraying, dip-coating, also can print the materials such as surface treated plastics film, paper, cardboard, natural fabric in flexographic presses.Film rub resistance, water-fast, resistance toly to rub, strong adhesion, bright in luster, and cost is lower.