CN108912832A - A kind of modified aqueous acrylic acid resin flexible version water-based ink and preparation method thereof - Google Patents
A kind of modified aqueous acrylic acid resin flexible version water-based ink and preparation method thereof Download PDFInfo
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- CN108912832A CN108912832A CN201810930635.XA CN201810930635A CN108912832A CN 108912832 A CN108912832 A CN 108912832A CN 201810930635 A CN201810930635 A CN 201810930635A CN 108912832 A CN108912832 A CN 108912832A
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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- 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
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/30—Inorganic compounds
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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Abstract
The invention discloses a kind of modified aqueous acrylic acid resin flexible version water-based inks and preparation method thereof, the raw material composition including following weight proportion：Modified aqueous acrylic acid resin binder 30-60%, pigment 15-25%, antisettling agent 0.1-2%, defoaming agent 0.1-2.0%, Antisepticize and mildew preventive 0.1-1.0%, dispersing agent 0.1-1.0%, solvent 20-50%, filler 1.0-5%, neutralizer 1.0-3.0%, thickener 0.1-1.0%；The present invention not only sets about from the synthesis of resin, including selection, technique and proportion etc., and by test of many times probed into each composition in water-based ink with the influence for comparing some performances of water-based ink, the rate of drying of the water-based ink of synthesis, glossiness and water-resistance are all relatively good.
Description
Technical field
The invention belongs to water-based ink technical fields, and in particular to a kind of modified aqueous acrylic acid resin flexible version water-based ink
And preparation method thereof.
Background technique
Water-based ink is a kind of novel ink to come into being in the environment of people increasingly pay close attention to low-carbon environment-friendly, tool
There is the unrivaled safety and environmental protection feature of other ink.Be mainly used in flexographic plate and intaglio printing, especially in recent years with
The fast development of flexible version printing, aqueous flexographic printing printing ink has obtained quick development, in some developed countries, 90% with
On flexographic plate all use water-based ink, its prospect is very wide.
Although water-based flexographic ink has fairly obvious advantage, but most of water-based ink of domestic production is with dry
The disadvantages such as dry speed is slow, water-resistance is poor, glossiness is low, these disadvantages also inhibit its fast development and utilization.These disadvantages
Mainly related to the auxiliary agent of the performance of resin used and ink, water-based acrylic resin is rapidly developed by its excellent performance
Meanwhile its some disadvantages also can not be ignored, for example film forming drying time is long, water resistance, stain resistance and solvent resistance are poor
Deng these all limit its development, so in order to make acrylic resin have wider application, it is necessary for being modified to it
's.
The Chinese invention patent of application number CN201510471014.6 discloses a kind of aqueous oil of flexographic plate of high speed printing
Ink and preparation method thereof, the component including following parts by weight：Acrylic acid not 30~40 parts of filming emulsion, acrylic acid filming emulsion 5
~10 parts, 15~20 parts of acrylic resin soln, 30~40 parts of aqueous color paste, 1~3 part of polyethylene wax, 1~2 part of coalescing agent,
0.3~1 part of levelling agent, 0.1~0.5 part of defoaming agent, 3~7 parts of deionized water and pH adjusting agent；Wherein acrylic acid not filming emulsion
All be made of single acrylic acid solution with acrylic acid filming emulsion, and it is general it is acrylic resin modified all can use two kinds
Monomer, one is hard soft monomer, another kind is function monomer, is showed from the soft or hard sense of film, when soft monomer is more, film performance
Soft, glass transition temperature is low, is not easy to form a film, surface tack；As the content of hard monomer increases, the surface property of film is improved, film
Hardness also increases, but when being added excessive, the cohesive force of polymer itself can be made decline, and film forming difficulty or even powder phenomenon-tion occurs,
The adhesive force and flexibility for making film so also decline.
Summary of the invention
According to the above-mentioned deficiencies of the prior art, the technical problem to be solved by the present invention is to propose a kind of modified water-soluble third
Olefin(e) acid resin flexible version water-based ink and preparation method thereof, in order to solve the above-mentioned technical problem or subproblem, what the present invention used
Technical solution is：
A kind of modified aqueous acrylic acid resin flexible version water-based ink, the raw material composition including following weight proportion：Modified water
Property acrylic resin binder 30-60%, pigment 15-25%, antisettling agent 0.1-2%, defoaming agent 0.1-2.0%, anti-corrosion it is anti-
Mould dose of 0.1-1.0%, dispersing agent 0.1-1.0%, solvent 20-50%, filler 1.0-5%, neutralizer 1.0-3.0%, thickener
0.1-1.0%.
Preferably, the pigment includes organic pigment and inorganic pigment, wherein inorganic pigment is mainly carbon black and titanium white
Powder；Organic pigment is mainly mordant pigment, azo pigment and phthalocyanine pigment.
Preferably, the antisettling agent is gas phase nano silica；Defoaming agent is organic silicone oil；Antisepticize and mildew preventive is
Dodecyl benzyl dimethyl ammonium chloride；Dispersing agent is alkyl sulfate sodium.
Preferably, the solvent is deionized water and isopropanol mixed liquor；Filler is wollastonite in powder；Neutralizer is ethyl alcohol
Amine and concentration are the mixed liquor of 10-20% ammonium hydroxide.
A kind of preparation method of modified aqueous acrylic acid resin flexible version water-based ink, mainly includes the following steps that：
(1) modified aqueous acrylic acid resin binder is prepared：In the four-hole boiling flask equipped with thermometer, condenser pipe and blender
It is middle that 1.2 grams of OP-10,0.8 gram of lauryl sodium sulfate, 35 grams of deionized waters, 0.5 gram of sodium bicarbonate are first added, use constant pressure addition
21.6 grams of methyl methacrylates, 14.4 grams of butyl acrylates, 1.5 grams of acrylic acid, 1 gram of acrylic acid hydroxyl is added in funnel while stirring
Propyl ester, heating water bath are warming up to 75-80 DEG C, and it is that 10% ammonium persulfate solution is warming up to after 30 minutes that 0.04 gram of concentration, which is added,
80-85 DEG C, start that 20 grams of deionized waters, 2.4 grams of methyl methacrylates, 1.6 grams of butyl acrylates, 2 grams of acrylic acid hydroxyls are added dropwise
Propyl ester and 0.16 gram of ammonium persulfate, control is at the uniform velocity added dropwise, and is added dropwise in three hours.80-90 DEG C of guarantor is warming up to after dripping off
Warm 1-2h accelerates mixing speed, and defoaming agent is added, and when temperature in reaction vessel is reduced to 40 DEG C or less, starts that neutralization is added dropwise
Agent until pH is 7~8, then is poured out, as water-based acrylic resin binder with 100 mesh gauzes are overanxious；
(2) master grind is prepared：By 30-60% modified aqueous acrylic acid resin binder, 20-50% solvent, 1.0-5%
Filler, 0.1-1% dispersing agent and 15-25% pigment are added in reaction kettle and mix, then by high speed disperser stir it is pre-dispersed, grind
Wear into standby color paste；
(3) by standby color paste and 0.1-2% antisettling agent, 0.1-1.0% Antisepticize and mildew preventive, 0.1-1.0% thickener
It is placed in ball mill and grinds, make granularity≤10 μm, to product testing, be packed and stored after items detection is qualified, be sealed and be placed on
Shady place saves.
Preferably, the quickening mixing speed, mixing speed are 15000-3000 revs/min, and the time is 10-25 points
Clock.
Compared with prior art, beneficial effects of the present invention：
1. the present invention is stablized by synthesis modification water-based acrylic resin, synthesis process, functional, simple process is closed
At the rate of drying of water-based ink, glossiness and water-resistance it is all relatively good.
2. common water borne ink is independently synthesized and is modified in its rate of drying of improvement and water-resistance, usually single passing through
Resin used, and influence of each auxiliary agent to its rate of drying and water-resistance in water-based ink is had ignored, on the other hand just only
The common resins for selecting matching degree not high by adding various auxiliary agents and improvement ink formulations, the present invention is not only from the conjunction of resin
At setting about, including selection, technique and proportion etc., and by test of many times probed into each composition in water-based ink with comparing water
Property some performances of ink influence, finally select optimal proportion with reach film forming drying time it is short, water resistance, stain resistance and
The preferable effect of solvent resistance.
3. using ammonium persulfate (APS) in the present invention as initiator carrys out synthesis modification water-based acrylic resin, this is mainly
Because ammonium persulfate belongs to heat decomposition type, when higher temperature, can decompose to give off rapidly oxygen and generate ammonium hydrogen sulfate, extra
Ammonium can be vapored away from air, keep polymer resin purer, and ammonium persulfate is used for water-based acrylic resin emulsion polymerization
When reaction, obtained lotion water resistance is preferable, thus manufactured ink setting speed is fast, water-resistance is good, glossiness is high.
Specific embodiment
It below by the description to embodiment, is described in further detail, to help those skilled in the art to this hair
Bright inventive concept, technical solution have more complete, accurate and deep understanding.
Embodiment 1
Red ink
1. preparing modified aqueous acrylic acid resin binder：In the four-hole boiling flask equipped with thermometer, condenser pipe and blender
It is middle that 1.2 grams of OP-10,0.8 gram of lauryl sodium sulfate, 35 grams of deionized waters, 0.5 gram of sodium bicarbonate are first added, use constant pressure addition
21.6 grams of methyl methacrylates, 14.4 grams of butyl acrylates, 1.5 grams of acrylic acid, 1 gram of acrylic acid hydroxyl is added in funnel while stirring
Propyl ester, heating water bath are warming up to 75-80 DEG C, and it is that 10% ammonium persulfate solution is warming up to after 30 minutes that 0.04 gram of concentration, which is added,
80-85 DEG C, start that 20 grams of deionized waters, 2.4 grams of methyl methacrylates, 1.6 grams of butyl acrylates, 2 grams of acrylic acid hydroxyls are added dropwise
Propyl ester and 0.16 gram of ammonium persulfate, control is at the uniform velocity added dropwise, and is added dropwise in three hours.80-90 DEG C of guarantor is warming up to after dripping off
Warm 2h accelerates mixing speed, and revolving speed is 1000 revs/min, stirs 10 minutes, organic silicone oil is added, drops to temperature in reaction vessel
When down to 40 DEG C or less, start that ethanol amine is added dropwise and concentration is the mixed liquor of 10-20% ammonium hydroxide, until pH is 7~8, then with 100 mesh
Gauze is overanxious to be poured out, as water-based acrylic resin binder；
2. preparing red pigment：It takes golden light bright red and permanent bordeaux is 3 in mass ratio:2 are uniformly mixed, and obtain red pigment；
3. preparing master grind：By 42% modified aqueous acrylic acid resin binder, 25% deionized water and isopropanol
Mixed liquor, 5% wollastonite in powder, 1% alkyl sulfate sodium and 20% red pigment are added in reaction kettle and mix, then pass through high speed point
Scattered machine stirring is pre-dispersed, is ground into standby color paste；
4. by standby color paste and 1% gas phase nano silica, 1.0% dodecyl benzyl dimethyl ammonium chloride, 1.0%
Thickener be placed in ball mill and grind, make granularity≤10 μm, to product testing, be packed and stored, seal after items detection is qualified
It is placed on shady place preservation well.
Embodiment 2
Huang Mo
1. preparing modified aqueous acrylic acid resin binder；
2. preparing yellow uitramarine：Taking benzidine yellow and consolidating forever orange is in mass ratio 1:1 is uniformly mixed, and obtains yellow uitramarine；
3. preparing master grind：By 39% modified aqueous acrylic acid resin binder, 30% deionized water and isopropanol
Mixed liquor, 3% wollastonite in powder, 0.5% alkyl sulfate sodium and 22% yellow uitramarine are added in reaction kettle and mix, then pass through high speed
Dispersion machine stirring is pre-dispersed, is ground into standby color paste；
4. by standby color paste and 1.7% gas phase nano silica, 0.3% dodecyl benzyl dimethyl ammonium chloride,
0.5% thickener, which is placed in ball mill, to be ground, and granularity≤10 μm are made, and to product testing, is packed and stored after items detection is qualified,
It is sealed and is placed on shady place preservation.
The preparation method is the same as that of Example 1 for modified aqueous acrylic acid resin binder in the present embodiment.
Embodiment 3
Lan Mo
1. preparing modified aqueous acrylic acid resin binder；
2. preparing blue pigment：Victoria pure blue and phthalocyanine blue are 2 in mass ratio:3 are uniformly mixed, and obtain blue pigment；
3. preparing master grind：By 40% modified aqueous acrylic acid resin binder, 27% deionized water and isopropanol
Mixed liquor, 4% wollastonite in powder, 1% alkyl sulfate sodium and 20% yellow uitramarine are added in reaction kettle and mix, then pass through high speed point
Scattered machine stirring is pre-dispersed, is ground into standby color paste；
4. by standby color paste and 2% gas phase nano silica, 1% dodecyl benzyl dimethyl ammonium chloride, 1% increasing
Thick dose is placed in ball mill and grinds, and makes granularity≤10 μm, to product testing, is packed and stored after items detection is qualified, is sealed and puts
It sets and is saved in shady place.
The preparation method is the same as that of Example 1 for modified aqueous acrylic acid resin binder in the present embodiment.
The performance test of embodiment 1-3 ink is shown in Table 1.
Table 1
| Project | Red ink | Huang Mo | Lan Mo |
| Tinting strength, tinting power (%) | 95 | 93 | 95 |
| Viscosity (Pas) | 0.2 | 0.17 | 0.15 |
| Glossiness (%) | 88 | 89 | 90 |
| Fineness (μm) | ≤10 | ≤10 | ≤10 |
| PH value | 8.9 | 8.8 | 9.0 |
| First stemness (mm/30s) | 20 | 22 | 18 |
| Alkaline-resisting, acidproof, water resistance | >=3 grades | >=3 grades | >=3 grades |
Ink dry times of the invention are short as shown in Table 1, the preferable effect of water resistance, stain resistance.
The present invention is exemplarily described above in conjunction with specific embodiment, it is clear that the present invention implements not by upper
The limitation of mode is stated, if the improvement for the various unsubstantialities that the inventive concept and technical scheme of the present invention carry out is used, or
It is not improved the conception and technical scheme of the invention are directly applied to other occasions, protection scope of the present invention it
It is interior.Protection scope of the present invention should be determined by the scope of protection defined in the claims.
Claims (6)
1. a kind of modified aqueous acrylic acid resin flexible version water-based ink, which is characterized in that the raw material group including following weight proportion
At：Modified aqueous acrylic acid resin binder 30-60%, pigment 15-25%, antisettling agent 0.1-2%, defoaming agent 0.1-
2.0%, Antisepticize and mildew preventive 0.1-1.0%, dispersing agent 0.1-1.0%, solvent 20-50%, filler 1.0-5%, neutralizer 1.0-
3.0%, thickener 0.1-1.0%.
2. a kind of modified aqueous acrylic acid resin flexible version water-based ink according to claim 1, which is characterized in that described
Pigment includes organic pigment and inorganic pigment, wherein inorganic pigment is mainly carbon black and titanium dioxide；Organic pigment is mainly color lake
Pigment, azo pigment and phthalocyanine pigment.
3. a kind of modified aqueous acrylic acid resin flexible version water-based ink according to claim 1, which is characterized in that described
Antisettling agent is gas phase nano silica；Defoaming agent is organic silicone oil；Antisepticize and mildew preventive is dodecyl dimethyl benzyl chloride
Change ammonium；Dispersing agent is alkyl sulfate sodium.
4. a kind of modified aqueous acrylic acid resin flexible version water-based ink according to claim 1, which is characterized in that described
Solvent is deionized water and isopropanol mixed liquor；Filler is wollastonite in powder；Neutralizer is ethanol amine and concentration is 10-20% ammonium hydroxide
Mixed liquor.
5. a kind of preparation method of modified aqueous acrylic acid resin flexible version water-based ink, which is characterized in that mainly include following step
Suddenly：
(1) modified aqueous acrylic acid resin binder is prepared：In the four-hole boiling flask equipped with thermometer, condenser pipe and blender first
1.2 grams of OP-10,0.8 gram of lauryl sodium sulfate, 35 grams of deionized waters, 0.5 gram of sodium bicarbonate is added, uses constant pressure funnel
21.6 grams of methyl methacrylates, 14.4 grams of butyl acrylates, 1.5 grams of acrylic acid, 1 gram of acrylic acid hydroxypropyl are added while stirring
Ester, heating water bath are warming up to 75-80 DEG C, and it is that 10% ammonium persulfate solution was warming up to 80- after 30 minutes that 0.04 gram of concentration, which is added,
85 DEG C, start that 20 grams of deionized waters, 2.4 grams of methyl methacrylates, 1.6 grams of butyl acrylates, 2 grams of hydroxypropyl acrylates are added dropwise
With 0.16 gram of ammonium persulfate, control is at the uniform velocity added dropwise, and is added dropwise in three hours.80-90 DEG C of heat preservation 1- is warming up to after dripping off
2h accelerates mixing speed, and defoaming agent is added, and when temperature in reaction vessel is reduced to 40 DEG C or less, starts that neutralizer is added dropwise, until
PH is 7~8, then is poured out with 100 mesh gauzes are overanxious, as water-based acrylic resin binder；
(2) master grind is prepared：30-60% modified aqueous acrylic acid resin binder, 20-50% solvent, 1.0-5% are filled out
Material, 0.1-1% dispersing agent and 15-25% pigment are added in reaction kettle and mix, then stir pre-dispersed, grinding by high speed disperser
At standby color paste；
(3) standby color paste and the thickener of 0.1-2% antisettling agent, 0.1-1.0% Antisepticize and mildew preventive, 0.1-1.0% are placed in
It is ground in ball mill, makes granularity≤10 μm, to product testing, be packed and stored after items detection is qualified, be sealed and be placed on darkness
Place saves.
6. a kind of preparation method of modified aqueous acrylic acid resin flexible version water-based ink according to claim 5, feature
It is, the quickening mixing speed, mixing speed is 15000-3000 revs/min, and the time is 10-25 minutes.
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| CN109777198A (en) * | 2019-02-13 | 2019-05-21 | 新昌县高纤纺织有限公司 | Environmentally friendly oil-soluble oil ink and its preparation process |
| CN113185633A (en) * | 2021-05-08 | 2021-07-30 | 深圳市安伯斯科技有限公司 | Acrylic acid copolymer emulsion, water-based ink and preparation method thereof |
| CN113665263A (en) * | 2021-09-10 | 2021-11-19 | 朱宏达 | Vacuum heat transfer printing flower film |
| CN114231101A (en) * | 2021-12-31 | 2022-03-25 | 佛山市南海区沙头才华化工有限公司 | Water-based antibacterial mildew inhibitor, preparation method thereof and antibacterial mildew-resistant brick |
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| CN109777198A (en) * | 2019-02-13 | 2019-05-21 | 新昌县高纤纺织有限公司 | Environmentally friendly oil-soluble oil ink and its preparation process |
| CN113185633A (en) * | 2021-05-08 | 2021-07-30 | 深圳市安伯斯科技有限公司 | Acrylic acid copolymer emulsion, water-based ink and preparation method thereof |
| CN113665263A (en) * | 2021-09-10 | 2021-11-19 | 朱宏达 | Vacuum heat transfer printing flower film |
| CN114231101A (en) * | 2021-12-31 | 2022-03-25 | 佛山市南海区沙头才华化工有限公司 | Water-based antibacterial mildew inhibitor, preparation method thereof and antibacterial mildew-resistant brick |
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Application publication date: 20181130 |
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