CN1181146C - Preparation method of covering emulsion used in water printing ink - Google Patents
Preparation method of covering emulsion used in water printing ink Download PDFInfo
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- CN1181146C CN1181146C CNB021520135A CN02152013A CN1181146C CN 1181146 C CN1181146 C CN 1181146C CN B021520135 A CNB021520135 A CN B021520135A CN 02152013 A CN02152013 A CN 02152013A CN 1181146 C CN1181146 C CN 1181146C
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Abstract
The present invention discloses a method for preparing concealed emulsion for aqueous printing ink. The method comprises: free radical emulsion copolymerization is carried out to monomers or unsaturated monomers in acrylic acid series in a step-by-step mode under the condition of a temperature of 60 to 90 DEG C, wherein acrylic resin with a high acid value and low molecular weight is used as dispersion resin, an anionic and nonionic integral surface active agent is used as an emulsifying agent, and persulphate is used as an initiating agent; synthetic latex grains are emulsion with a three-layer structure of 'a core/a middle layer/a shell'; the emulsion is swelled by alkali materials at a higher temperature; the emulsion obtains favorable concealing performance by certain optical effect. Aqueous printing ink prepared from the concealed emulsion as connection materials of the method of the present invention has good concealing performance, and has the advantages of full printing layer, luster, brilliant color, good weatherability and difficult discoloration. The compatibility of the emulsion and color paste and the viscosity stability of the emulsion and a system compounded by a modified aqueous rosin resin solution are good.
Description
Affiliated technical field
The present invention relates to the preparation method of the opacifying property emulsion of a kind of used for water color ink.
Background technology
Along with the continuous enhancing of people's environmental consciousness, the packing box of more and more commodity begins to adopt the water color ink printing.Domestic traditional water color ink manufacturer uses modified soluble Gum Rosin solution as low-melting ink vehicle, is mixed with water color ink with mill base.Modified soluble Gum Rosin low price, strong coloring force, but anti-marquis, poor water resistance, the printing ink over-all properties of preparation is relatively poor.In recent years, begin to gradually adopt the low-melting ink vehicle of ACRYLIC EMULSION as water color ink.Can promote the dispersion of pigment in water on the one hand, strengthen the printing adaptability of printing ink; On the other hand, with the anti-marquis of printing ink, the water-tolerant of this emulsion preparation, can improve the class of water color ink greatly.But some printing materials (for example water lustering oil) ACRYLIC EMULSION commonly used is used for preparing water color ink, and performance is not so good, mainly is that the printing ink tinting strength of preparation is bad, and is opacifying property poor because very transparent after these emulsion dryings, needs to add a lot of fillers.Printed layers gloss is low in addition, especially more seems intensely dark on some fluting board trs, so the opacifying property acrylic type emulsion of Development and Production just has been fit to the needs in market very much.
Summary of the invention
The object of the present invention is to provide the preparation method of the opacifying property emulsion of a kind of used for water color ink, opacifying property emulsion with this method preparation is bright in luster as the water color ink that connects the material preparation, and weather resistance is good, and is not easy to change, face, add the material consumption few, the consistency of emulsion and mill base is good.
The preparation method of the opacifying property emulsion of a kind of used for water color ink provided by the invention may further comprise the steps:
(1) be comonomer with acrylic monomer and non-acrylic acid series unsaturated monomer, with molecular weight is 4000～12000, acid number is that 170～250 acrylic resin is a dispersion resin, with sulfo-succinic acid polyoxyethylene octyl phenol sodium salt surface active agent is emulsifying agent, with the persulphate is initiator, is the comonomer that slowly splashes into the nuclear part that accounts for comonomer total amount 3～8% under 60～90 ℃ of conditions in temperature, carries out the free radical emulsion copolymerization, 0.5 dripped off in～1 hour, and be incubated to emulsion blueing light;
(2) drip the comonomer in the middle layer account for comonomer total amount 7～20% again, dripped off in 0.5～1 hour, be incubated 1 hour;
(3) dropping at last accounts for the comonomer of the shell of comonomer total amount 70～90%, the dropping time is 4～7 hours, to drip molecular weight after 1 hour simultaneously be 4000～12000 dripping shell monomers, and acid number is the aqueous solution of 170～250 acrylic resin, and the dropping time is 2～3 hours;
(4) in copolymer emulsion, add ammoniacal liquor down at 60～90 ℃, regulate pH value to 7～10, be incubated 1～2 hour;
(5) the cooling back adds auxiliary agent in copolymer emulsion, promptly gets the opacifying property emulsion of used for water color ink of the present invention after filtration;
In the above-mentioned steps, by weight percentage, the consumption of acrylic resin is 5～15%, the total amount of comonomer is 30～55%, and the content summation of the comonomer of the comonomer of its center part, the comonomer in middle layer and shell is 100%, and the consumption of sulfo-succinic acid polyoxyethylene octyl phenol sodium salt is 0.5～3%, the consumption of persulphate is 0.2～2.5%, the consumption of water is 30～55%, and the consumption of ammoniacal liquor is 2～4%, and the consumption of auxiliary agent is 0.2～0.6%.
In the comonomer of the present invention, acrylic monomer is selected from vinylformic acid, methacrylic acid, acrylic or methacrylic acid C
8-C
16Alkyl ester, acrylic or methacrylic acid C
1-C
4Alkyl ester or glycidyl methacrylate; Non-acrylic acid series unsaturated monomer is selected from acrylamide, n-methylolacrylamide, Vinylstyrene or trimethylene bisacrylamide.Auxiliary agent of the present invention is sanitas and defoamer.
Synthetic emulsion particle of the present invention has " nuclear/middle layer/shell " three-decker, and its center partial monosomy amount is 3～8% of a monomer total amount, and the second-order transition temperature of nuclear is higher, surpasses 100 ℃, and the volume of nuclear is less, and diameter is about 1/10～1/9 of shell external diameter; The middle layer amount of monomer is about 7～20% of monomer total amount, and the middle layer second-order transition temperature is relatively low, is approximately 40～55 ℃, and the mean diameter in middle layer is about 1/4～1/3 of shell external diameter; The shell monomers amount is about 70～90% of monomer total amount, and the second-order transition temperature of shell has also surpassed 100 ℃.The nuclear of emulsion particle and shell are all harder, and middle layer softer relatively (second-order transition temperature is lower), and contain more acrylic or methacrylic acid in the polymerization single polymerization monomer, thus a large amount of carboxyls introduced.In the later stage of synthetic emulsion, add certain amount of ammonia water, the carboxyl reaction in ammonia and middle layer, make molecular chain fully stretch, a large amount of spaces can occur, the moisture in the emulsion constantly fills the remarkable swelling in middle layer by the shell of emulsion particle, size increases, and the emulsion particle median size can enlarge several times.When emulsion film was dry, the moisture in middle layer is volatilization thereupon also, thereby made emulsion particle the low density middle layer of a part hollow occur.Since the density difference of each layer of emulsion particle structure, light in atmosphere/shell, shell/middle layer, the middle layer/three interfaces of nuclear can reflect, and the interface refraction coefficient has nothing in common with each other, form the intensive diffuse scattering thus, make film opaque, outward appearance shows as white, thereby has had opacifying property.
In the preparation of the opacifying property emulsion of the present invention, when dripping shell monomers, drips lower molecular weight, high acid value acrylic resin soln simultaneously in the later stage.This lower molecular weight, high acid value resin are as dispersion resin, its hydrophilic carboxyl can make emulsion particle stably be scattered in the system, strengthened emulsion store and use in stability and with the composite viscosity stability of system afterwards of water-soluble rosin resin solution, and what of this resin demand have direct influence to the gloss and the final water color ink printed matter of resin after the emulsion drying; When the negatively charged ion of introducing and the consumption of the two-in-one emulsifying agent of nonionic also can be than common letex polymerizations the consumption of emulsifying agent lacks, and has reduced the water sensitivity of the printed layers that emulsifying agent brings.If this lower molecular weight, high acid value acrylic resin join system too early, can influence polymerization mechanism, it is opacifying property that emulsion is lost.
When carrying out the core/shell type letex polymerization, the phenomenon of " phase reversion " appears easily.In nuclear and shell monomers, select some polyene-based unsaturated monomers for use, take place partial cross-linkedly when making polymerization between molecular chain, then can significantly strengthen the force of cohesion of nuclear and shell, reduce interpenetrating between nuclear, shell and the middle layer two-phase, avoid taking place " phase reversion ".In order to guarantee the stability of emulsion, the polyene-based unsaturated monomer of selecting for use is generally Vinylstyrene etc., and consumption is not more than 5% of nuclear monomer total amount usually, is preferably 1%～3%.Simultaneously for can be when the swelling treatment alkaline matter such as ammoniacal liquor arrive the middle layer by shell, generally also add a small amount of acrylic or methacrylic acid in the shell monomers.
The opacifying property emulsion of used for water color ink of the present invention obtains by emulsion polymerisation process, and its principal feature is: (1) emulsion particle is " nuclear/middle layer/shell " three-decker; (2) nuclear is harder with shell, and the middle layer is softer and be rich in carboxyl; (3) at high temperature make the abundant swelling in emulsion particle middle layer with alkaline matter, the emulsion particle median size can enlarge several times after the swelling; (4) when emulsion film was dry, the atmosphere/shell of emulsion particle, shell/middle layer, middle layer/three interfaces of nuclear can produce certain optical effect, make film opaque, and outward appearance shows as white, glossy, has had opacifying property; (5) later stage is introduced lower molecular weight, high acid value acrylic resin as dispersion resin, can strengthen emulsion store and use in stability and with the composite viscosity stability of system afterwards of water-soluble rosin resin solution, this in addition resin also can improve the gloss of water color ink printed layers.
The opacifying property emulsion of the present invention's preparation is a kind of type material that can satisfy printing packaging market to high-grade water color ink demand, with this opacifying property acrylic type emulsion is to connect to expect that the water color ink that is mixed with has well covering property, printed layers is plentiful, bright in luster, weather resistance is good, not easy to change, face, to add the material consumption few, the consistency of emulsion and mill base and also fine with the viscosity stability of the composite system afterwards of modified soluble Gum Rosin solution.
The invention will be further described below in conjunction with specific embodiment, and umber related among the embodiment is weight part.
Embodiment 1
In the there-necked flask that has agitator, thermometer, add 71 parts of deionized waters, 9 parts of ammoniacal liquor are warming up to 60 ℃, and adding 20 parts of molecular weight is 5000, acid number is 240 acrylic resin, high-speed stirring, 60 ℃ of insulations 1 hour, solid content is 20% acrylic resin soln, viscosimetric is 20～30 seconds, and the pH value is 8～9.
Embodiment 2
In the four-hole boiling flask that has prolong, Dropping feeder, agitator, thermometer, add 39 parts of deionized waters and 2 parts of sulfo-succinic acid polyoxyethylene octyl phenol sodium salts, be heated to 75 ℃, add 0.4 part of Potassium Persulphate, drip following mix monomer: 4 parts of methyl methacrylates, 0.2 part of n-methylolacrylamide added in 1 hour, in 75 ℃ of insulations 1 hour; Drip following mix monomer again: 3.5 parts of methyl methacrylates, 3.5 parts of ethyl propenoates, 2.1 parts of methacrylic acids added in 1 hour, in 75 ℃ of insulations 1 hour; Drip following mix monomer again: 27.5 parts of methyl methacrylates, 0.7 part of methacrylic acid, 0.5 part of n-methylolacrylamide added in 5 hours, in 75 ℃ of insulations 1 hour; Dripping the third part monomer after one hour, drip 12 part 20% acrylic resin soln simultaneously, added in 2 hours.Be cooled to add 3 parts of ammoniacal liquor below 60 ℃, be warming up to 80 ℃ again, be incubated 1 hour.Be cooled to below 45 ℃, add 0.2 part of auxiliary agent such as defoamer, filter through 120 eye mesh screens, get opacifying property emulsion, solid content is 48.4%.
Embodiment 3
The middle layer mix monomer is by 3.1 parts of methyl methacrylates, 4.3 parts of butyl acrylates, 2.4 parts of compositions of vinylformic acid, other prescription is identical with embodiment 2 with technology, opacifying property emulsion, solid content is 49.1%.
Embodiment 4
The shell mix monomer is by 27.3 parts of methyl methacrylates, 0.6 part in vinylformic acid, 0.5 part of Vinylstyrene, other prescription is identical with embodiment 2 with technology, opacifying property emulsion, solid content is 48.1%.
Embodiment 5
The high acid value, the low-molecular-weight acrylic resin soln that add 6 part 20%, other prescription is identical with embodiment 2 with technology, opacifying property emulsion, dry back resin is opaque, has opacifying property, but matt.
Application Example
Get 32 parts of opacifying property emulsions, 21 parts of filming emulsions, 6 parts of water-soluble rosin resin solutions, 4 parts of wax emulsions, 32.3 parts of mill bases, 2.7 parts of Virahols, 0.5 part of flow agent, 0.5 part of defoamer, 1 part in water, preparation obtains water color ink.This water color ink stability in storage and viscosity stability are good, and the printing back is bright in luster and dried clean form and aspect can be provided, and brown kraft paper is had splendid covering property.
Claims (3)
1, the preparation method of the opacifying property emulsion of a kind of used for water color ink may further comprise the steps:
(1) be comonomer with acrylic monomer and non-acrylic acid series unsaturated monomer, with molecular weight is 4000～12000, acid number is that 170～250 acrylic resin is a dispersion resin, with sulfo-succinic acid polyoxyethylene octyl phenol sodium salt surface active agent is emulsifying agent, with the persulphate is initiator, is the comonomer that slowly splashes into the nuclear part that accounts for comonomer total amount 3～8% under 60～90 ℃ of conditions in temperature, carries out the free radical emulsion copolymerization, 0.5 dripped off in～1 hour, and be incubated to emulsion blueing light;
(2) drip the comonomer in the middle layer account for comonomer total amount 7～20% again, dripped off in 0.5～1 hour, be incubated 1 hour;
(3) dropping at last accounts for the comonomer of the shell of comonomer total amount 70～90%, the dropping time is 4～7 hours, to drip molecular weight after 1 hour simultaneously be 4000～12000 dripping shell monomers, and acid number is the aqueous solution of 170～250 acrylic resin, and the dropping time is 2～3 hours;
(4) in copolymer emulsion, add ammoniacal liquor down at 60～90 ℃, regulate pH value to 7～10, be incubated 1～2 hour;
(5) the cooling back adds auxiliary agent in copolymer emulsion, promptly gets the opacifying property emulsion of used for water color ink of the present invention after filtration;
In the above-mentioned steps, by weight percentage, the consumption of acrylic resin is 5～15%, the total amount of comonomer is 30～55%, and the content summation of the comonomer of the comonomer of its center part, the comonomer in middle layer and shell is 100%, and the consumption of sulfo-succinic acid polyoxyethylene octyl phenol sodium salt is 0.5～3%, the consumption of persulphate is 0.2～2.5%, the consumption of water is 30～55%, and the consumption of ammoniacal liquor is 2～4%, and the consumption of auxiliary agent is 0.2～0.6%.
2, the preparation method of the opacifying property emulsion of used for water color ink according to claim 1 is characterized in that: described acrylic monomer is selected from vinylformic acid, methacrylic acid, acrylic or methacrylic acid C
8-C
16Alkyl ester, acrylic or methacrylic acid C
1-C
4Alkyl ester or glycidyl methacrylate; Described non-acrylic acid series unsaturated monomer is selected from acrylamide, n-methylolacrylamide, Vinylstyrene or trimethylene bisacrylamide.
3, the preparation method of the opacifying property emulsion of used for water color ink according to claim 1 is characterized in that: described auxiliary agent is sanitas and defoamer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021520135A CN1181146C (en) | 2002-11-20 | 2002-11-20 | Preparation method of covering emulsion used in water printing ink |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021520135A CN1181146C (en) | 2002-11-20 | 2002-11-20 | Preparation method of covering emulsion used in water printing ink |
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| CN1181146C true CN1181146C (en) | 2004-12-22 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381531C (en) * | 2005-09-14 | 2008-04-16 | 北京高盟化工有限公司 | Composite adhesive for soft wrapper and its preparation method |
| CN101982494B (en) * | 2010-09-07 | 2012-05-23 | 百利合化工（中山）有限公司 | Preparation method of covering hollow microsphere emulsion for printing coating |
| CN103183995B (en) * | 2013-03-18 | 2016-01-06 | 福建省利得彩环保科技有限公司 | Water-based paint compositions |
| CN104151937B (en) * | 2014-07-07 | 2016-08-17 | 杭州海维特化工科技有限公司 | A kind of PE optical cable and cable special ink jet numbering machine ink and preparation method |
| CN109735226B (en) * | 2018-12-14 | 2020-08-14 | 珠海市润星泰电器有限公司 | Coating material for light alloy pulping and preparation method thereof |
| CN113072669B (en) * | 2020-01-03 | 2022-02-18 | 万华化学集团股份有限公司 | Acrylate swellable rheological modifier with core-shell structure and preparation method thereof |
| CN115612344B (en) * | 2022-10-20 | 2024-07-05 | 湖北中烟工业有限责任公司 | Covering flexography process |
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