CN109777198A - Environmentally friendly oil-soluble oil ink and its preparation process - Google Patents
Environmentally friendly oil-soluble oil ink and its preparation process Download PDFInfo
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- CN109777198A CN109777198A CN201910113276.3A CN201910113276A CN109777198A CN 109777198 A CN109777198 A CN 109777198A CN 201910113276 A CN201910113276 A CN 201910113276A CN 109777198 A CN109777198 A CN 109777198A
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Abstract
The present invention discloses a kind of environmentally friendly oil-soluble oil ink and its preparation process, including following raw material: 55-75 parts acrylic resin modified, 40-55 parts of environmentally friendly pigments and fillers, 70-95 parts of n-butanols, 55-75 parts of dehydrated alcohols, 15-25 parts of dispersing agents, 15-20 parts of thickeners, 35-50 parts of hyperbranched poly glycerol, 5-15 parts of polypropylene glycerol aethers；The present invention is during preparing oil-soluble oil ink using n-butanol as solvent, it is reacted acrylic resin modified with hyperbranched poly glycerol, form glycidyl methacrylate, glycidyl methacrylate had not only had the carbon-carbon double bond in acrylic resin but also had had epoxy group, epoxy group can react with the hydroxyl on polypropylene glycerol aether surface, increase the chain branches in glycidyl methacrylate, so that the polarity of glycidyl methacrylate enhances, hydrogen bond can be formed with hydrone, further enhance the solubility property of ink.
Description
Technical field
The invention belongs to Printing ink producing technical field, specially a kind of environmentally friendly oil-soluble oil ink and its preparation process.
Background technique
Ink is the important materials for printing, it is expressed the pattern and text on stock by printing or air brushing.Oil
It include main component and auxiliary element in ink, they equably mix and form a kind of stickiness colloidal fluid through repeat-rolling.By
The composition such as link stuff (resin), pigment, filler, auxiliary agent and solvent.For books and periodicals, packing and decorating, building decoration and electronic circuit
The various printings such as plate.As social demand increases, ink variety and yield also respective extension and growth.
With the rapid growth of China's economic, people's living standard is further increased, consumer to food, medicine, tobacco and wine,
Cosmetics, toy etc. are packed for ink and propose high requirement.Oil-soluble oil ink almost without volatile organic compounds row
It puts, there is environmentally friendly, nontoxic, energy saving, emission reduction green character, meet the requirement of consumer.In recent years, China is to food, drug
The safety of packaging is made that regulation, and the status for promoting ink to be printed on China's printing market rises year by year, and the market share is increasingly
Expand, there is preferable prospect.
But the disadvantages such as the oil-soluble oil ink slow drying speed in existing market, weather resistance are poor, glossiness is low, these are lacked
Point also inhibits the fast development and application of oil-soluble oil ink.
Summary of the invention
In order to overcome above-mentioned technical problem, the present invention provides a kind of environmentally friendly oil-soluble oil ink and its preparation process.It is making
It using n-butanol as solvent during standby oil-soluble oil ink, reacts, is formed with hyperbranched poly glycerol by acrylic resin modified
Glycidyl methacrylate, glycidyl methacrylate had not only had the carbon-carbon double bond in acrylic resin but also had had ring
Oxygen groups, epoxy group can react with the hydroxyl on polypropylene glycerol aether surface, increase methyl propenoic acid glycidyl
Chain branches in ester can form hydrogen bond with hydrone, further so that the polarity of glycidyl methacrylate enhances
Enhance the solubility property of ink.
The purpose of the present invention can be achieved through the following technical solutions:
Environmentally friendly oil-soluble oil ink is made of following raw material: 55-75 parts acrylic resin modified, 40-55 parts of environmental protection
Pigments and fillers, 70-95 parts of n-butanols, 55-75 parts of dehydrated alcohols, 15-25 parts of dispersing agents, 15-20 parts of thickeners, 35-50 parts of over-expenses
Change polyglycereol, 5-15 parts of polypropylene glycerol aethers；
The environmental protection oil-soluble oil ink is made of following steps:
Step S1, it is added acrylic resin modified in the beaker equipped with n-butanol, 45 DEG C of heating water baths at the uniform velocity stir
Hyperbranched poly glycerol is added after 15min, is warming up to 60 DEG C, stirs 5min, it is spare to make A liquid；
Step S2, dehydrated alcohol, dispersing agent are added in three-necked flask, 60 DEG C of heating water baths, magnetic agitation 30min adds
Enter polypropylene glycerol aether, be warming up to 75 DEG C after polypropylene glycerol aether dissolution, thickener is added, at the uniform velocity stirring 10min, makees
B liquid；
Step S3, A liquid is poured into B liquid, at the uniform velocity stirring 5min, 5mL10% sodium bicarbonate solution is added, obtained after reacting 2h
To mixed liquor, mixed liquor is dispersed with dispersion machine after ultrasonic 30min, the revolving speed for controlling dispersion machine is 4000r/min；
Step S4, the mixed liquor after dispersion is centrifuged by the centrifuge of 12000r/min, obtains sediment, with nothing
Water-ethanol washs sediment, and sediment is poured into beaker, and being transferred to vacuum degree is -0.10MPa, and temperature is 80 DEG C
Dry 10h in vacuum oven；
Step S5, it pours into ball mill, high speed ball milling is carried out with the revolving speed of 1600r/min, environmental protection oil-soluble oil ink is made.
Further, described acrylic resin modified to be made by the following method:
(1) 20mL methyl methacrylate, 15mL acrylic acid, 10mL ethyl acrylate are added in beaker after mixing, are turned
It moves in the four-hole boiling flask equipped with 100mL deionized water, at the uniform velocity stirring 5min, 5mL lauric monoglyceride and 5mL10% is added
Potassium peroxydisulfate, 50 DEG C of heating water baths react 2.5h；
(2) 10mL methyl methacrylate, 5mL acrylic acid, 5mL ethyl acrylate is added, 80 DEG C are warming up to, in this temperature
Lower reaction 30min is cooled to 50 DEG C after keeping the temperature 2h, and 10% sodium hydroxide solution is added and adjusts pH, until pH=8, filtering, obtain
Acrylic resin is put into 60 DEG C of drying boxes dry 1h, is added in ball mill after acrylic resin is washed with deionized, with
The revolving speed of 800r/min carries out ball milling；
(3) tartaric acid is added in the beaker equipped with deionized water, ball is added after winestone acid dissolution in 75 DEG C of heating water baths
Acrylic resin after mill is made acrylic resin modified after ultrasonic disperse 2h, by acrylic resin modified taking-up, uses deionization
Water cleaning is placed in 70 DEG C of drying boxes dry 1h, and the weight ratio for controlling tartaric acid and acrylic resin is 5: 1.
The present invention is with methyl methacrylate for hard soft monomer, and acrylic acid, ethyl acrylate are function monomer, to pass through
Emulsion polymerization prepares acrylic resin, and the acrylic resin of preparation has excellent hardness, glossiness and good weatherability
Can, but the ink attachment since the surface tension of water is larger, to substrate in use prepared by acrylic resin
Power is poor, will lead to ink layer and defect occurs, and wetting and dispersion of the acrylic resin to pigments and fillers during preparing ink
Property it is poor, will lead to ink occur loose colour and layering phenomena such as.
The present invention is modified acrylic resin by tartaric acid, the main linear structure of acrylic resin, the degree of branching
Lower, with the hydroxyl on acrylic resin surface polycondensation reaction can occur for the carboxyl and hydroxyl of tartaric acid itself institute band, by tartaric acid
It is grafted on acrylic resin surface, is formed simultaneously a kind of tridimensional network, by the hydrogen bond of formation by tartaric acid and acrylic acid
Resin-bonded together, reduces the interfacial tension between tartaric acid and acrylic resin, so that the tridimensional network formed
Free radical number is reduced in structure, can be improved the hydrophily and stability of the ink of acrylic resin modified preparation.
Further, the environmentally friendly pigments and fillers are made by the following method:
(1) 2g dodecyl sodium sulfate is added in the three-necked flask equipped with 50mL styrene, stands 30min, dodecane
Base sodium sulfonate is completely dissolved, and 1g sodium peroxydisulfate is added in the beaker equipped with 10mL deionized water, by the sodium peroxydisulfate in beaker
Solution is added in three-necked flask, at the uniform velocity stirring 20min, is warming up to 70 DEG C, is reacted at this temperature to not flowing back, is stood
2h is centrifuged with centrifuge, and polystyrene microsphere template is made；
(2) 20mL ethyl orthosilicate is added in 50mL dehydrated alcohol, 1mL25% ammonium hydroxide is added, tri- ethyl alcohol of 1.5mL is added dropwise
Amine, at the uniform velocity stirring are until solution is clarified；
(3) polystyrene microsphere template is added in clear solution, after ultrasonic disperse 30min, with turning for 10000r/min
Speed carries out high speed centrifugation, and precipitating is taken out, and with washes of absolute alcohol 3 times, dioxy is made after being put into 100 DEG C of drying boxes dry 4h
SiClx microballoon；
(4) silicon dioxide microsphere and hard fire colour are uniformly mixed and are placed in Muffle furnace, after calcining 30min at 250 DEG C
It takes out, standing 2h, which is added in ball mill, to be ground, is sieved, and the environmentally friendly pigments and fillers that partial size is 7-80 μm, silica is made
The weight ratio of microballoon and hard fire colour is 3: 1, and the revolving speed of ball mill is 2000r/min.
Further, the dispersing agent is one or more of HPMA, polyethylene glycol 200, polyethylene wax.
Further, the thickener is one of polyvinyl alcohol, polyethylene glycol oxide, polyvinylpyrrolidone or several
Kind.
The preparation process of environmentally friendly oil-soluble oil ink, includes the following steps:
Step S1, it is added acrylic resin modified in the beaker equipped with n-butanol, 45 DEG C of heating water baths at the uniform velocity stir
Hyperbranched poly glycerol is added after 15min, is warming up to 60 DEG C, stirs 5min, it is spare to make A liquid；
Step S2, dehydrated alcohol, dispersing agent are added in three-necked flask, 60 DEG C of heating water baths, magnetic agitation 30min adds
Enter polypropylene glycerol aether, be warming up to 75 DEG C after polypropylene glycerol aether dissolution, thickener is added, at the uniform velocity stirring 10min, makees
B liquid；
Step S3, A liquid is poured into B liquid, at the uniform velocity stirring 5min, 5mL10% sodium bicarbonate solution is added, obtained after reacting 2h
To mixed liquor, mixed liquor is dispersed with dispersion machine after ultrasonic 30min, the revolving speed for controlling dispersion machine is 4000r/min；
Step S4, the mixed liquor after dispersion is centrifuged by the centrifuge of 12000r/min, obtains sediment, with nothing
Water-ethanol washs sediment, and sediment is poured into beaker, and being transferred to vacuum degree is -0.10MPa, and temperature is 80 DEG C
Dry 10h in vacuum oven；
Step S5, it pours into ball mill, high speed ball milling is carried out with the revolving speed of 1600r/min, environmental protection oil-soluble oil ink is made.
Beneficial effects of the present invention:
(1) present invention during preparing oil-soluble oil ink using n-butanol as solvent, will it is acrylic resin modified with overspend
Change polyglycereol to be reacted, form glycidyl methacrylate, glycidyl methacrylate had both had acrylic acid tree
Carbon-carbon double bond in rouge has epoxy group again, and epoxy group can react with the hydroxyl on polypropylene glycerol aether surface, increases
Add the chain branches in glycidyl methacrylate, it, can be with so that the polarity of glycidyl methacrylate enhances
Hydrone forms hydrogen bond, further enhances the solubility property of ink.
(2) present invention is modified it after preparing acrylic resin, passes through hydroxyl and wine on acrylic resin surface
Tartaric acid molecules are grafted on acrylic resin surface, after grafting by the polycondensation reaction that hydroxyl and carboxyl in stone acid molecule occur
Acrylic resin itself contain a large amount of polar functional groups simultaneously in highly polar, there are two the tartaric acid molecules of formation are contained due to it
Asymmetric carbon atom, so that tartaric acid so that forming a large amount of hydrogen bonds between strand increases soluble oil there are many isomers
The viscosity of ink, and improve its glossiness.
(3) present invention prepares polystyrene microsphere template by dodecyl sodium sulfate and styrene, passes through polyphenyl later
Ethylene microsphere template prepares silicon dioxide microsphere, so that the environmentally friendly pigments and fillers finally prepared exist with nano shape, has
Good coloring effect and not easy to reunite, two can be effectively prevented by preparing silicon dioxide microsphere by polystyrene microsphere template
Silicon oxide microsphere is reunited, and pigments and fillers is avoided to reunite during preparing ink, is caused ink uneven, is improved oil
The coloring effect of ink.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, all other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Embodiment 1
Environmentally friendly oil-soluble oil ink is made of following raw material: 55 parts acrylic resin modified, and 40 parts of environmentally friendly face are filled out
Material, 70 parts of n-butanols, 55 parts of dehydrated alcohols, 15 parts of HPMA, 15 parts of polyvinylpyrrolidones, 35 parts of hyperbranched poly glycerol, 5 parts poly-
Oxypropylene glycerin ether；
The environmental protection oil-soluble oil ink is made of following steps:
Step S1, it is added acrylic resin modified in the beaker equipped with n-butanol, 45 DEG C of heating water baths at the uniform velocity stir
Hyperbranched poly glycerol is added after 15min, is warming up to 60 DEG C, stirs 5min, it is spare to make A liquid；
Step S2, dehydrated alcohol, HPMA are added in three-necked flask, 60 DEG C of heating water baths, magnetic agitation 30min is added
Polypropylene glycerol aether is warming up to 75 DEG C after polypropylene glycerol aether dissolution, polyvinylpyrrolidone is added, at the uniform velocity stirs
10min makees B liquid；
Step S3, A liquid is poured into B liquid, at the uniform velocity stirring 5min, 5mL10% sodium bicarbonate solution is added, obtained after reacting 2h
To mixed liquor, mixed liquor is dispersed with dispersion machine after ultrasonic 30min, the revolving speed for controlling dispersion machine is 4000r/min；
Step S4, the mixed liquor after dispersion is centrifuged by the centrifuge of 12000r/min, obtains sediment, with nothing
Water-ethanol washs sediment, and sediment is poured into beaker, and being transferred to vacuum degree is -0.10MPa, and temperature is 80 DEG C
Dry 10h in vacuum oven；
Step S5, it pours into ball mill, high speed ball milling is carried out with the revolving speed of 1600r/min, environmental protection oil-soluble oil ink is made.
It is acrylic resin modified to be made by the following method:
(1) 20mL methyl methacrylate, 15mL acrylic acid, 10mL ethyl acrylate are added in beaker after mixing, are turned
It moves in the four-hole boiling flask equipped with 100mL deionized water, at the uniform velocity stirring 5min, 5mL lauric monoglyceride and 5mL10% is added
Potassium peroxydisulfate, 50 DEG C of heating water baths react 2.5h；
(2) 10mL methyl methacrylate, 5mL acrylic acid, 5mL ethyl acrylate is added, 80 DEG C are warming up to, in this temperature
Lower reaction 30min is cooled to 50 DEG C after keeping the temperature 2h, and 10% sodium hydroxide solution is added and adjusts pH, until pH=8, filtering, obtain
Acrylic resin is put into 60 DEG C of drying boxes dry 1h, is added in ball mill after acrylic resin is washed with deionized, with
The revolving speed of 800r/min carries out ball milling；
(3) tartaric acid is added in the beaker equipped with deionized water, ball is added after winestone acid dissolution in 75 DEG C of heating water baths
Acrylic resin after mill is made acrylic resin modified after ultrasonic disperse 2h, by acrylic resin modified taking-up, uses deionization
Water cleaning is placed in 70 DEG C of drying boxes dry 1h, and the weight ratio for controlling tartaric acid and acrylic resin is 5: 1.
Environmentally friendly pigments and fillers are made by the following method:
(1) 2g dodecyl sodium sulfate is added in the three-necked flask equipped with 50mL styrene, stands 30min, dodecane
Base sodium sulfonate is completely dissolved, and 1g sodium peroxydisulfate is added in the beaker equipped with 10mL deionized water, by the sodium peroxydisulfate in beaker
Solution is added in three-necked flask, at the uniform velocity stirring 20min, is warming up to 70 DEG C, is reacted at this temperature to not flowing back, is stood
2h is centrifuged with centrifuge, and polystyrene microsphere template is made；
(2) 20mL ethyl orthosilicate is added in 50mL dehydrated alcohol, 1mL25% ammonium hydroxide is added, tri- ethyl alcohol of 1.5mL is added dropwise
Amine, at the uniform velocity stirring are until solution is clarified；
(3) polystyrene microsphere template is added in clear solution, after ultrasonic disperse 30min, with turning for 10000r/min
Speed carries out high speed centrifugation, and precipitating is taken out, and with washes of absolute alcohol 3 times, dioxy is made after being put into 100 DEG C of drying boxes dry 4h
SiClx microballoon；
(4) silicon dioxide microsphere and hard fire colour are uniformly mixed and are placed in Muffle furnace, after calcining 30min at 250 DEG C
It takes out, standing 2h, which is added in ball mill, to be ground, is sieved, and the environmentally friendly pigments and fillers that partial size is 7-80 μm, silica is made
The weight ratio of microballoon and hard fire colour is 3: 1, and the revolving speed of ball mill is 2000r/min.
Embodiment 2
Environmentally friendly oil-soluble oil ink is made of following raw material: 60 parts acrylic resin modified, and 42 parts of environmentally friendly face are filled out
Material, 80 parts of n-butanols, 60 parts of dehydrated alcohols, 18 parts of HPMA, 16 parts of polyvinylpyrrolidones, 40 parts of hyperbranched poly glycerol, 8 parts poly-
Oxypropylene glycerin ether；
The environmental protection oil-soluble oil ink is made of following steps:
Step S1, it is added acrylic resin modified in the beaker equipped with n-butanol, 45 DEG C of heating water baths at the uniform velocity stir
Hyperbranched poly glycerol is added after 15min, is warming up to 60 DEG C, stirs 5min, it is spare to make A liquid；
Step S2, dehydrated alcohol, HPMA are added in three-necked flask, 60 DEG C of heating water baths, magnetic agitation 30min is added
Polypropylene glycerol aether is warming up to 75 DEG C after polypropylene glycerol aether dissolution, polyvinylpyrrolidone is added, at the uniform velocity stirs
10min makees B liquid；
Step S3, A liquid is poured into B liquid, at the uniform velocity stirring 5min, 5mL10% sodium bicarbonate solution is added, obtained after reacting 2h
To mixed liquor, mixed liquor is dispersed with dispersion machine after ultrasonic 30min, the revolving speed for controlling dispersion machine is 4000r/min；
Step S4, the mixed liquor after dispersion is centrifuged by the centrifuge of 12000r/min, obtains sediment, with nothing
Water-ethanol washs sediment, and sediment is poured into beaker, and being transferred to vacuum degree is -0.10MPa, and temperature is 80 DEG C
Dry 10h in vacuum oven；
Step S5, it pours into ball mill, high speed ball milling is carried out with the revolving speed of 1600r/min, environmental protection oil-soluble oil ink is made.
Embodiment 3
Environmentally friendly oil-soluble oil ink is made of following raw material: 70 parts acrylic resin modified, and 50 parts of environmentally friendly face are filled out
Material, 90 parts of n-butanols, 70 parts of dehydrated alcohols, 22 parts of HPMA, 18 parts of polyvinylpyrrolidones, 46 parts of hyperbranched poly glycerol, 12 parts
Polypropylene glycerol aether；
The environmental protection oil-soluble oil ink is made of following steps:
Step S1, it is added acrylic resin modified in the beaker equipped with n-butanol, 45 DEG C of heating water baths at the uniform velocity stir
Hyperbranched poly glycerol is added after 15min, is warming up to 60 DEG C, stirs 5min, it is spare to make A liquid；
Step S2, dehydrated alcohol, HPMA are added in three-necked flask, 60 DEG C of heating water baths, magnetic agitation 30min is added
Polypropylene glycerol aether is warming up to 75 DEG C after polypropylene glycerol aether dissolution, polyvinylpyrrolidone is added, at the uniform velocity stirs
10min makees B liquid；
Step S3, A liquid is poured into B liquid, at the uniform velocity stirring 5min, 5mL10% sodium bicarbonate solution is added, obtained after reacting 2h
To mixed liquor, mixed liquor is dispersed with dispersion machine after ultrasonic 30min, the revolving speed for controlling dispersion machine is 4000r/min；
Step S4, the mixed liquor after dispersion is centrifuged by the centrifuge of 12000r/min, obtains sediment, with nothing
Water-ethanol washs sediment, and sediment is poured into beaker, and being transferred to vacuum degree is -0.10MPa, and temperature is 80 DEG C
Dry 10h in vacuum oven；
Step S5, it pours into ball mill, high speed ball milling is carried out with the revolving speed of 1600r/min, environmental protection oil-soluble oil ink is made.
Embodiment 4
Environmentally friendly oil-soluble oil ink is made of following raw material: 75 parts acrylic resin modified, and 55 parts of environmentally friendly face are filled out
Material, 95 parts of n-butanols, 75 parts of dehydrated alcohols, 25 parts of HPMA, 20 parts of polyvinylpyrrolidones, 50 parts of hyperbranched poly glycerol, 15 parts
Polypropylene glycerol aether；
The environmental protection oil-soluble oil ink is made of following steps:
Step S1, it is added acrylic resin modified in the beaker equipped with n-butanol, 45 DEG C of heating water baths at the uniform velocity stir
Hyperbranched poly glycerol is added after 15min, is warming up to 60 DEG C, stirs 5min, it is spare to make A liquid；
Step S2, dehydrated alcohol, HPMA are added in three-necked flask, 60 DEG C of heating water baths, magnetic agitation 30min is added
Polypropylene glycerol aether is warming up to 75 DEG C after polypropylene glycerol aether dissolution, polyvinylpyrrolidone is added, at the uniform velocity stirs
10min makees B liquid；
Step S3, A liquid is poured into B liquid, at the uniform velocity stirring 5min, 5mL10% sodium bicarbonate solution is added, obtained after reacting 2h
To mixed liquor, mixed liquor is dispersed with dispersion machine after ultrasonic 30min, the revolving speed for controlling dispersion machine is 4000r/min；
Step S4, the mixed liquor after dispersion is centrifuged by the centrifuge of 12000r/min, obtains sediment, with nothing
Water-ethanol washs sediment, and sediment is poured into beaker, and being transferred to vacuum degree is -0.10MPa, and temperature is 80 DEG C
Dry 10h in vacuum oven；
Step S5, it pours into ball mill, high speed ball milling is carried out with the revolving speed of 1600r/min, environmental protection oil-soluble oil ink is made.
Comparative example 1
This comparative example compared with Example 1, is not modified acrylic resin, the preparation method is as follows:
(1) 20mL methyl methacrylate, 15mL acrylic acid, 10mL ethyl acrylate are added in beaker after mixing, are turned
It moves in the four-hole boiling flask equipped with 100mL deionized water, at the uniform velocity stirring 5min, 5mL lauric monoglyceride and 5mL10% is added
Potassium peroxydisulfate, 50 DEG C of heating water baths react 2.5h；
(2) 10mL methyl methacrylate, 5mL acrylic acid, 5mL ethyl acrylate is added, 80 DEG C are warming up to, in this temperature
Lower reaction 30min is cooled to 50 DEG C after keeping the temperature 2h, and 10% sodium hydroxide solution is added and adjusts pH, until pH=8, filtering, obtain
Acrylic resin is put into 60 DEG C of drying boxes dry 1h, is added in ball mill after acrylic resin is washed with deionized, with
The revolving speed of 800r/min carries out ball milling.
Comparative example 2
Hyperbranched poly glycerol is not added compared with Example 1 for this comparative example, the preparation method is as follows:
Step S1, it is added acrylic resin modified in the beaker equipped with n-butanol, 45 DEG C of heating water baths at the uniform velocity stir
15min is warming up to 60 DEG C, stirs 5min, it is spare to make A liquid；
Step S2, dehydrated alcohol, HPMA are added in three-necked flask, 60 DEG C of heating water baths, magnetic agitation 30min is added
Polypropylene glycerol aether is warming up to 75 DEG C after polypropylene glycerol aether dissolution, polyvinylpyrrolidone is added, at the uniform velocity stirs
10min makees B liquid；
Step S3, A liquid is poured into B liquid, at the uniform velocity stirring 5min, 5mL10% sodium bicarbonate solution is added, obtained after reacting 2h
To mixed liquor, mixed liquor is dispersed with dispersion machine after ultrasonic 30min, the revolving speed for controlling dispersion machine is 4000r/min；
Step S4, the mixed liquor after dispersion is centrifuged by the centrifuge of 12000r/min, obtains sediment, with nothing
Water-ethanol washs sediment, and sediment is poured into beaker, and being transferred to vacuum degree is -0.10MPa, and temperature is 80 DEG C
Dry 10h in vacuum oven；
Step S5, it pours into ball mill, high speed ball milling is carried out with the revolving speed of 1600r/min, environmental protection oil-soluble oil ink is made.
Comparative example 3
The present embodiment is a kind of oil-soluble oil ink in market.
Acid resistance, alkali resistance, drying property and the gloss of environmentally friendly oil-soluble oil ink are prepared to embodiment 1-4 and comparative example 1-3
Degree is tested for the property, as a result as shown in table 1 below.
Acid resistance: the environmentally friendly oil-soluble oil ink of embodiment 1-4 and comparative example 1-3 preparation is scraped into sample on drawdown sheet or is printed as reality
Ground version, dry at normal temperature the small item for being cut into 2 × 4cm is separately immersed in 10% dilute hydrochloric acid solution for 24 hours, is taken out after impregnating 20h
It is compared with specimen page is not impregnated, observes discoloration.
Alkali resistance: the environmentally friendly oil-soluble oil ink of embodiment 1-4 and comparative example 1-3 preparation is scraped into sample on drawdown sheet or is printed as reality
Ground version, dry at normal temperature the small item for being cut into 2 × 4cm is separately immersed in 10% sodium hydroxide solution for 24 hours, is taken after impregnating 20h
Out with do not impregnate specimen page and compare, observe discoloration.
Drying property: referring to GB/T13217.5-2008 " the first stemness method of inspection of liquid ink ", to embodiment 1-4 and comparison
Example 1-3 prepares environmentally friendly oil-soluble oil ink and is tested.
Glossiness: referring to GB/T13217.2-2009 " the liquid ink gloss method of inspection ", to embodiment 1-4 and comparative example
1-3 prepares environmentally friendly oil-soluble oil ink and is tested.
Table 1
, it can be seen that the oil-soluble oil ink of embodiment 1-2 preparation is placed in 10% dilute hydrochloric acid solution from upper table 1, impregnate
20h can slightly change colour, and the oil-soluble oil ink of embodiment 3-4 preparation is non-discolouring, and the oil-soluble oil ink of comparative example 1-3 preparation can occur
Obvious discoloration；The oil-soluble oil ink of embodiment 1-2 preparation is placed in 10% sodium hydroxide solution, is impregnated 20h, can slightly be changed colour, real
The oil-soluble oil ink for applying 3-4 preparation is non-discolouring, and comparative example 1-2 can occur obviously to change colour, and comparative example 3 can serious discoloration；Implement
Just stemness is in 18-25 (μm/30s) range for the oil-soluble oil ink of example 1-4 preparation, at the beginning of the oil-soluble oil ink of comparative example 1-3 preparation
Stemness is in 15-17 (μm/30s) range；The oil-soluble oil ink glossiness of embodiment 1-4 preparation is between 87-95% range, comparison
The oil-soluble oil ink glossiness of example 1-3 preparation is between 78-85% range；So oil-soluble oil ink prepared by the present invention has well
Acid-fast alkali-proof performance, excellent first stemness can and higher glossiness.
In the description of this specification, the description of reference term " one embodiment ", " example ", " specific example " etc. means
Particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained at least one implementation of the invention
In example or example.In the present specification, schematic expression of the above terms may not refer to the same embodiment or example.
Moreover, particular features, structures, materials, or characteristics described can be in any one or more of the embodiments or examples to close
Suitable mode combines.
Above content is only citing made for the present invention and explanation, affiliated those skilled in the art are to being retouched
The specific embodiment stated does various modifications or additions or is substituted in a similar manner, and without departing from invention or surpasses
More range defined in the claims, is within the scope of protection of the invention.
Claims (6)
1. environmentally friendly oil-soluble oil ink, which is characterized in that be made of following raw material: 55-75 parts are acrylic resin modified,
40-55 parts of environmentally friendly pigments and fillers, 70-95 parts of n-butanols, 55-75 parts of dehydrated alcohols, 15-25 parts of dispersing agents, 15-20 parts of thickeners,
35-50 parts of hyperbranched poly glycerol, 5-15 parts of polypropylene glycerol aethers；
The environmental protection oil-soluble oil ink is made of following steps:
Step S1, it is added acrylic resin modified in the beaker equipped with n-butanol, 45 DEG C of heating water baths, at the uniform velocity stirring 15min
Hyperbranched poly glycerol is added afterwards, is warming up to 60 DEG C, stirs 5min, it is spare to make A liquid；
Step S2, dehydrated alcohol, dispersing agent are added in three-necked flask, 60 DEG C of heating water baths, magnetic agitation 30min, are added poly-
Oxypropylene glycerin ether is warming up to 75 DEG C after polypropylene glycerol aether dissolution, thickener is added, at the uniform velocity stirring 10min, makees B liquid；
Step S3, A liquid is poured into B liquid, at the uniform velocity stirring 5min, 5mL10% sodium bicarbonate solution is added, is mixed after reacting 2h
Liquid is closed, mixed liquor is dispersed with dispersion machine after ultrasonic 30min, the revolving speed for controlling dispersion machine is 4000r/min；
Step S4, the mixed liquor after dispersion is centrifuged by the centrifuge of 12000r/min, obtains sediment, with anhydrous second
Alcohol washs sediment, and sediment is poured into beaker, and being transferred to vacuum degree is -0.10MPa, the vacuum that temperature is 80 DEG C
Dry 10h in drying box；
Step S5, it pours into ball mill, high speed ball milling is carried out with the revolving speed of 1600r/min, environmental protection oil-soluble oil ink is made.
2. environmental protection oil-soluble oil ink according to claim 1, which is characterized in that described acrylic resin modified by such as lower section
Method is made:
(1) 20mL methyl methacrylate, 15mL acrylic acid, 10mL ethyl acrylate are added in beaker after mixing, are transferred to
In four-hole boiling flask equipped with 100mL deionized water, 5mL lauric monoglyceride and 5mL10% over cure is added at the uniform velocity stirring 5min
Sour potassium, 50 DEG C of heating water baths react 2.5h；
(2) 10mL methyl methacrylate, 5mL acrylic acid, 5mL ethyl acrylate is added, is warming up to 80 DEG C, at this temperature instead
30min is answered, is cooled to 50 DEG C after keeping the temperature 2h, 10% sodium hydroxide solution is added and adjusts pH, until pH=8, filtering, obtain propylene
Acid resin is put into 60 DEG C of drying boxes dry 1h, is added in ball mill after acrylic resin is washed with deionized, with
The revolving speed of 800r/min carries out ball milling；
(3) tartaric acid is added in the beaker equipped with deionized water, 75 DEG C of heating water baths, after ball milling is added after winestone acid dissolution
Acrylic resin, be made acrylic resin modified after ultrasonic disperse 2h, it is clear with deionized water by acrylic resin modified taking-up
It washes and is placed in 70 DEG C of drying boxes dry 1h, the weight ratio for controlling tartaric acid and acrylic resin is 5: 1.
3. environmental protection oil-soluble oil ink according to claim 1, which is characterized in that the environmental protection pigments and fillers are made by the following method
At:
(1) 2g dodecyl sodium sulfate is added in the three-necked flask equipped with 50mL styrene, stands 30min, dodecyl sulphur
Sour sodium is completely dissolved, and 1g sodium peroxydisulfate is added in the beaker equipped with 10mL deionized water, by the sodium peroxydisulfate solution in beaker
It is added in three-necked flask, at the uniform velocity stirring 20min, is warming up to 70 DEG C, reacted at this temperature to not flowing back, stand 2h, used
Centrifuge is centrifuged, and polystyrene microsphere template is made；
(2) 20mL ethyl orthosilicate is added in 50mL dehydrated alcohol, 1mL25% ammonium hydroxide is added, 1.5mL triethanolamine is added dropwise,
At the uniform velocity stirring is until solution is clarified；
(3) by polystyrene microsphere template be added clear solution in, after ultrasonic disperse 30min, with the revolving speed of 10000r/min into
Row high speed centrifugation takes out precipitating, and with washes of absolute alcohol 3 times, silica is made after being put into 100 DEG C of drying boxes dry 4h
Microballoon；
(4) silicon dioxide microsphere and hard fire colour are uniformly mixed and are placed in Muffle furnace, taken out after calcining 30min at 250 DEG C,
Stand 2h to be added in ball mill and grinds, is sieved, be made the environmentally friendly pigments and fillers that partial size is 7-80 μm, silicon dioxide microsphere with
The weight ratio of hard fire colour is 3: 1, and the revolving speed of ball mill is 2000r/min.
4. environmental protection oil-soluble oil ink according to claim 1, which is characterized in that the dispersing agent is HPMA, polyethylene glycol
200, one or more of polyethylene wax.
5. environmental protection oil-soluble oil ink according to claim 1, which is characterized in that the thickener is polyvinyl alcohol, polyoxy
Change one or more of ethylene, polyvinylpyrrolidone.
6. the preparation process of environmentally friendly oil-soluble oil ink, which comprises the steps of:
Step S1, it is added acrylic resin modified in the beaker equipped with n-butanol, 45 DEG C of heating water baths, at the uniform velocity stirring 15min
Hyperbranched poly glycerol is added afterwards, is warming up to 60 DEG C, stirs 5min, it is spare to make A liquid；
Step S2, dehydrated alcohol, dispersing agent are added in three-necked flask, 60 DEG C of heating water baths, magnetic agitation 30min, are added poly-
Oxypropylene glycerin ether is warming up to 75 DEG C after polypropylene glycerol aether dissolution, thickener is added, at the uniform velocity stirring 10min, makees B liquid；
Step S3, A liquid is poured into B liquid, at the uniform velocity stirring 5min, 5mL10% sodium bicarbonate solution is added, is mixed after reacting 2h
Liquid is closed, mixed liquor is dispersed with dispersion machine after ultrasonic 30min, the revolving speed for controlling dispersion machine is 4000r/min；
Step S4, the mixed liquor after dispersion is centrifuged by the centrifuge of 12000r/min, obtains sediment, with anhydrous second
Alcohol washs sediment, and sediment is poured into beaker, and being transferred to vacuum degree is -0.10MPa, the vacuum that temperature is 80 DEG C
Dry 10h in drying box；Step S5, it pours into ball mill, high speed ball milling is carried out with the revolving speed of 1600r/min, obtained environmental protection can
Soluble ink.
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| CN110015850A (en) * | 2019-05-30 | 2019-07-16 | 长沙集智创新工业设计有限公司 | A kind of ceramic glaze and preparation method thereof |
| CN110423543A (en) * | 2019-08-14 | 2019-11-08 | 程浩源 | A kind of coil coating and preparation method thereof based on silicone alkyd |
| CN110437537A (en) * | 2019-08-13 | 2019-11-12 | 江苏汉光实业股份有限公司 | Polypropylene BOPP color alternation agent |
| US20200291253A1 (en) * | 2019-03-12 | 2020-09-17 | Unist(Ulsan National Institute Of Science And Technology) | Ink composition for bioprinting and hydrogel formed from the same |
| CN112592620A (en) * | 2020-12-29 | 2021-04-02 | 苏州创亚材料科技有限公司 | Plate washing liquid for flexible resin plate and preparation method thereof |
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