A kind of raw lacquer ink solidified for digital spray printing and UV and its modulator approach
Technical field
The present invention relates to a kind of for digital spray printing and the raw lacquer ink and its modulator approach of UV solidifications, belong to digital
Multiple technical fields such as ink-jet printing technology, UV curing technologies, raw lacquer.Small-bore spray is cannot be used for because itself is sticky for raw lacquer
The defects of painting, by modification to raw lacquer and ink realize paint skill colored drawing made from simple Traditional Man to traditional handicraft and
Digitlization is combined the transformation of production.
Background technology
By taking raw lacquer as an example, the chemical composition of raw lacquer is mainly laccol(60%~70%), urushipolysaccharide(5%~7%), laccase
(<1.0%)And moisture(20%~30%).Raw lacquer paint film have prominent durability, high-decoration, antibiotic property, oxidation stability,
The premium properties such as corrosion resistance and environment friendly, is widely used.But raw lacquer is because its Coating technology cycle is long, cost is high, effect
Rate is low, has very strong sensitization, alkaline-resisting and UV resistant poor and is difficult to spraying coating process requirement height and complex procedures, in day
Often it is difficult to the condition requirement for meeting modern industrial process in production.Main Ingredients and Appearance in raw lacquer is laccol, and laccol is adjacent benzene two
The derivative of phenol, there are two phenolic hydroxyl groups, and the long side chain of C containing more than one=C double bonds on phenyl ring, it is anti-that a variety of chemistry can be carried out
Should.Hydroxyl is the seeking group of ortho para substitution reaction on phenyl ring, and hydroxyl is in itself and C=C double bonds of side chain are all Yi Qihua
Learn the active point of reaction.
And digital spray printing technology is one of most fast technical field of Developing, it is a kind of contactless, no pressure, without print
The digital imaging technology of version.UV ink has organic volatile zero-emission, low energy consumption in curable print technology, is suitable for respectively
Kind of stock, instant drying and it is moist before ink-jet, to shower nozzle without blocking the features such as.At present in printing industry, photocuring technology
It is a kind of relatively advanced new technology, for photocuring technology again mainly based on ultraviolet light photocuring, remaining also has infrared light, visible
Photocuring etc..UV solidifications refer to the energy using ultraviolet, the molecule of ink vehicle is produced polymerization, are solidify ink droplet one
Kind technology, have and dry rapidly, can online assignment;Non-volatility solvent, reduces environmental pollution;Save energy resource consumption;Printing is steady
The advantages that qualitative good.It is also a kind of that raw lacquer is combined for woodwork industry with digital spray printing technology, UV curing technologies
New opportunity.
Prepolymer is the main film forming substance in ink, and its performance determines the main performance of ink film forming.And light is consolidated
Typically there are C=C double bonds and epoxide group in the prepolymer of carburetion ink, can further react under light illumination.And the laccol in raw lacquer
Can also carry out it is epoxide modified, by raw lacquer reshaping turn into serve as a kind of prepolymer, be deployed into a kind of UV light-curable inks, make this oil
Ink has the advantages of both raw lacquer and ink are common, has unprecedented meaning.
It is domestic at present that raw lacquer is very limited with research that digital spray printing technology combines, do not find UV ink
Combine research and the patent document for digital spray printing technology and UV curing technologies with raw lacquer and modified raw lacquer.
The content of the invention
Proposed by the present invention is a kind of raw lacquer ink and its modulator approach for digital spray printing and UV solidification, its purpose master
If overcome traditional raw lacquer can not from jet-printing equipment shower nozzle under gush out, easily block shower nozzle, and hardening time length lacks
Fall into, with reference to the modulated process of UV ink, modified raw lacquer is combined with UV ink manufacturing technologies, be modulated into it is a kind of both can number sprayed
Print, does not block shower nozzle, new " the raw lacquer ink " that can solidify again by UV, " raw lacquer ink " that allotment obtains is had raw lacquer concurrently
With the premium properties of both UV ink, realize that raw lacquer covers with paint, lacquer, colour wash, etc. field and combines and innovate with the interdisciplinary of digital spray printing technical field,
Meet modern industrial process demand.New resin and ink formulation are synthesized with new reaction mechanism so that " the raw linseed oil of allotment
Ink " can spray in the case of not blocking shower nozzle from digital ink-jet printing equipment, and moment UV photocuring, have raw lacquer and
The premium properties of both UV ink, the defects of overcoming original technology.
The technical solution of the present invention:
A kind of raw lacquer ink solidified for digital spray printing with UV, is made up of following raw materials according and its mass percent:UV-
LED ink 40%-90%, laccol 2%-50%, epoxy resin 0-20%, aldehyde compound 0.01%-25%, acrylic monomer 0.5%-
20%, diluent 1%-60%, catalyst 0.05%-3%, auxiliary agent 0-5%, the percentage sum of above-mentioned raw materials is 100%.
A kind of modulator approach for digital spray printing and the raw lacquer ink of UV solidifications, comprise the following steps:
1)With dimethylbenzene three first from safe and comfortable paint, flat interest paint, entrance of the city paint, hair dam paint, Qinling Mountains paint or other raw lacquer
With quality 1 in mouth flask:1 ratio extraction laccol, takes supernatant liquor after standing, obtain laccol xylene solution or with ethanol with
Acetone extraction;
2)Then in laccol solution placing response kettle, 10%-50% aldehyde compound being added, by temperature control in 30-
70 DEG C carry out reaction 0.2-2h, and cross-linking reaction stops reaction after reaching requirement;
3)Reaction terminates rear persistently overheating dehydration, and temperature reaches 136 DEG C of water and purified, and obtains laccol aldehyde polymer;
4)The laccol air aldehyde resin of gained is continued to put in a kettle, adds a certain amount of epoxy resin and polymerization inhibitor,
Control temperature carries out reaction 0.1-2h at 35-70 DEG C, and reaction stops reaction after terminating, persistently overheating dehydration, obtains laccol epoxy
Resin;
5)In the three-necked flask equipped with agitator, condenser pipe, constant pressure funnel and thermometer, a certain amount of paint is added
Phenol epoxy resin and polymerization inhibitor, it is slowly stirred and is heated to 70 DEG C, then the mixed liquor of acrylic acid and catalyst is slowly added dropwise, heating,
Stirring, 95 DEG C are warming up to, strict controlling reaction temperature, is dropped after reacting 1h every 25min sampling and testing reaction system acid numbers, acid number
Stop reaction after to 5mgKOH/g, cooling obtains laccol epoxy acrylate;
6)In the three-necked flask equipped with agitator, reflux condensing tube, constant pressure funnel and thermometer, add a certain amount of
Ethanol after be heated with stirring to its reflux temperature(About 85 DEG C), after backflow is stable, about 2/5 propylene is dripped in 20min
Acrylic monomer.Drip after about crossing 15-20min, then start that the laccol epoxy acrylate dissolved and remaining propylene is added dropwise
Acrylic monomer, 1-3h is added dropwise;After being added dropwise, 80-85 DEG C of insulation reaction 2h is warming up to, it is middle to add in right amount light-initiated simultaneously
Agent;Then, 50 DEG C are cooled to, agitation and dropping ammoniacal liquor or NaOH solution are neutralized to pH7-8, and then insulated and stirred 20-30min goes out
Material;
7)The resin of gained is put into agitator, adds a certain amount of UV ink stirring 10-30min, then ultrasonic disperse
15-30min, obtain resin ink basis blend;
8)Select to be allocated in suitable diluent and auxiliary agent addition system, ultrasonic 0-15min, is obtained after mixing
UV available for jet-printing equipment solidifies " raw lacquer ink ".
Advantages of the present invention and innovative point:Overcome raw lacquer and modified raw lacquer can not spray printing obstruction shower nozzle and hardening time length
The problem of, manufactured " raw lacquer ink " can not only directly be "printed" to substrate surface by jet-printing equipment, and more
The defects of traditional raw lacquer and modified paint drying condition is harsh and time-consuming has been mended, can be by UV light instantaneous solidifications, whole process is not
More than 30 seconds, do mechanization operation can be achieved.Meanwhile manufactured " raw lacquer ink " both remained original raw lacquer paint film adhesion it is high,
Acidproof, alkaline-resisting, water-fast, oil resistant, it is wear-resisting, glossiness is high the advantages of, while paint solution inherits the perfect glossiness of UV ink, color
Coloured silk, instantaneous solidification, the advantages of shower nozzle, low stain, spray printing quality resistance good, suitable for various base materials is not blocked, gathered UV-
The advantages of LED ink is with both modified raw lacquers, synthesis technique is simple, condition is easily controllable, paint film property is good, can be widely applied for
The fields such as decoration, furniture, building, electronics, machinery, chemical industry, the present invention creatively applies " digital spray printing technology " and " UV is solid
Change technology ", and traditional handicraft is combined, realize the integrated innovation of digital spray printing technology so that paint skill colored drawing from simple traditional people
Work makes the transformation that production is combined to traditional handicraft and digitlization.
Embodiment
1. it is a kind of for digital spray printing and the raw lacquer ink of UV solidifications, it is characterized in that by following raw materials according and its mass percent
Composition:UV-LED ink 40%-90%, laccol 2%-50%, epoxy resin 0-20%, aldehyde compound 0.01%-25%, acrylic compounds
Monomer 0.5%-20%, diluent 1%-60%, catalyst 0.05%-3%, auxiliary agent 0-5%, the percentage sum of above-mentioned raw materials is 100%.
The UV-LED ink is UV ink, and main component includes:Light trigger, pigment, diluting monomer, prepolymer and help
Agent, it can solidify immediately under LED light source irradiation.
The laccol is from one or more kinds of paints in safe and comfortable paint, flat interest paint, entrance of the city paint, hair dam paint, Qinling Mountains paint
Extracted with xylene solution;Wherein, safe and comfortable paint:Flat interest paint:The mass ratio of entrance of the city paint is 1:1.5:1, Ankang paint:Paint in the Qinling Mountains
For 1:0.5, entrance of the city paint:Hair dam paint:The mass ratio of Qinling Mountains paint is 1.5:1:0.5, decoct disk fraction more than 65%, the matter of laccol content
Amount is than being more than 50%.
The aldehyde compound is the one or more in formaldehyde, furfural, phenolic aldehyde, metaformaldehyde, wherein, formaldehyde:Furfural
Mass ratio be 1:0.5, formaldehyde:The mass ratio of metaformaldehyde is 1.5:1.
The acrylic monomer is hexanediyl ester, tri (propylene glycol) diacrylate, neopentyl glycol two
Acrylate, triethylene-glycol diacrylate, phthalic acid diethanol diacrylate, the propylene of trimethylolpropene three
One or two or more kinds in acid esters.Wherein mass ratio is hexanediyl ester:Phthalic acid diethanol diacrylate
Ester:The mass ratio of neopentylglycol diacrylate is 1:2:1, triethylene-glycol diacrylate:Tripropylene glycol dipropyl
Olefin(e) acid ester:The mass ratio of trimethylolpropene triacrylate is 1:1:1.
The diluent is dimethylbenzene, ethanol, acetone, cyclohexanone, anti-plain boiled water(Ethylene glycol monobutyl ether, the fourth of ethylene glycol one
Ether), solvent naphtha(IP2028)In one or more, wherein, dimethylbenzene:The mass ratio of ethanol is 2:1, cyclohexanone:Third
The mass ratio of ketone is 2:1.
The catalyst is one in ammoniacal liquor, ammonium chloride, potassium hydroxide, barium hydroxide, calcium hydroxide, tertiary amines organic base
Kind or more than two kinds, wherein, ammonium chloride:The mass ratio of potassium hydroxide is 1:0.5, the mass ratio of barium hydroxide and calcium hydroxide is
2:1。
Described auxiliary agent is dispersant, light trigger, sensitising agent, defoamer, polymerization inhibitor, wetting agent or levelling agent.
A kind of modulator approach for digital spray printing and the raw lacquer ink of UV solidifications, comprise the following steps:
1)With dimethylbenzene three first from safe and comfortable paint, flat interest paint, entrance of the city paint, hair dam paint, Qinling Mountains paint or other raw lacquer
With quality 1 in mouth flask:1 ratio extraction laccol, takes supernatant liquor after standing, obtain laccol xylene solution or with ethanol with
Acetone extraction;
2)Then in laccol solution placing response kettle, 10%-50% aldehyde compound being added, by temperature control in 30-
70 DEG C carry out reaction 0.2-2h, and cross-linking reaction stops reaction after reaching requirement;
3)Reaction terminates rear persistently overheating dehydration, and temperature reaches 136 DEG C of water and purified, and obtains laccol aldehyde polymer;
4)The laccol air aldehyde resin of gained is continued to put in a kettle, adds a certain amount of epoxy resin and polymerization inhibitor,
Control temperature carries out reaction 0.1-2h at 35-70 DEG C, and reaction stops reaction after terminating, persistently overheating dehydration, obtains laccol epoxy
Resin;
5)In the three-necked flask equipped with agitator, condenser pipe, constant pressure funnel and thermometer, a certain amount of paint is added
Phenol epoxy resin and polymerization inhibitor, it is slowly stirred and is heated to 70 DEG C, then the mixed liquor of acrylic acid and catalyst is slowly added dropwise, heating,
Stirring, 95 DEG C are warming up to, strict controlling reaction temperature, is dropped after reacting 1h every 25min sampling and testing reaction system acid numbers, acid number
Stop reaction after to 5mgKOH/g, cooling obtains laccol epoxy acrylate;
6)In the three-necked flask equipped with agitator, reflux condensing tube, constant pressure funnel and thermometer, add a certain amount of
Ethanol after be heated with stirring to 85 DEG C of its reflux temperature, after backflow is stable, 2/5 acrylic compounds list is dripped in 20min
Body;After dripping 15-20min, then start that the laccol epoxy acrylate dissolved and remaining acrylic monomer is added dropwise,
1-3h is added dropwise;After being added dropwise, 80-85 DEG C of insulation reaction 2h is warming up to, it is middle to add appropriate light trigger simultaneously;Then,
50 DEG C are cooled to, agitation and dropping ammoniacal liquor or NaOH solution are neutralized to pH7-8, and then insulated and stirred 20-30min discharges;
7)The resin of gained is put into agitator, adds a certain amount of UV ink stirring 10-30min, then ultrasonic disperse
15-30min, obtain resin ink basis blend;
8)Select to be allocated in suitable diluent and auxiliary agent addition system, ultrasonic 0-15min, is obtained after mixing
UV available for jet-printing equipment solidifies " raw lacquer ink.
The above of the present invention is described in further detail below by way of specific embodiment.But this should not be managed
The scope solved as the above-mentioned theme of the present invention is only limitted to following instance.All technologies realized based on the above of the present invention are belonged to
The technical scope of the present invention.
Embodiment 1
In a kind of the raw lacquer ink and its modulator approach for digital spray printing and UV solidifications of the present embodiment, the matter of each component
It is as follows to measure percentage:
Ingredient names |
Mass percent(%) |
Laccol |
10 |
Furfural |
2 |
Epoxy resin |
3 |
Ammoniacal liquor |
0.25 |
Cyclohexanone |
13 |
UV ink |
70 |
Dispersant |
0.05 |
Polymerization inhibitor |
0.05 |
Light trigger |
0.15 |
Hexanediyl ester |
1.5 |
By above-mentioned mass ratio formula, the laccol select painted from safe and comfortable paint, flat interest paint, entrance of the city paint, hair dam paint, the Qinling Mountains or
One or more kinds of extractions of paint produced by other areas, decoct disk fraction more than 65%, and laccol content is more than 50%.
By above-mentioned mass ratio formula, by laccol solution and furfural placing response kettle, nitrogen is passed through, temperature control is at 60 DEG C
Left and right carries out reaction 0.5-1h, and the dehydration that then heats up obtains urushiol-furfural resin.Again epoxy resin is added in urushiol-furfural resin
Laccol epoxy resin is obtained, acrylic monomers and dispersant stirring is subsequently added into, is put into after filtering with UV ink and appropriate amount of addition agent
Agitator stirring, ultrasonic disperse, ultrasonic 15min after mixing, obtain raw lacquer ink.
Embodiment 2
In a kind of the raw lacquer ink and its modulator approach for digital spray printing and UV solidifications of the present embodiment, the matter of each component
It is as follows to measure percentage:
Ingredient names |
Mass percent(%) |
Laccol |
12 |
Formaldehyde |
3 |
Epoxy resin |
5 |
Barium hydroxide solution |
0.3 |
Tertiary phenyl amines organic base |
0.2 |
Dimethylbenzene |
15.2 |
Polymerization inhibitor |
0.05 |
Dispersant |
0.05 |
Light trigger |
0.2 |
UV ink |
63 |
Acrylate |
1 |
By above-mentioned mass ratio formula, the laccol select painted from safe and comfortable paint, flat interest paint, entrance of the city paint, hair dam paint, the Qinling Mountains or
One or more kinds of extractions of paint produced by other areas, decoct disk fraction more than 65%, and laccol content is more than 50%.
By above-mentioned mass ratio formula, by laccol solution and formaldehyde placing response kettle, enter in temperature control at 60 DEG C or so
Row reaction 0.5-1h, cross-linking reaction stop reaction after reaching requirement.Reaction terminates rear persistently overheating dehydration, and temperature reaches 136 DEG C
Left and right water purifies, and obtains Urushiol-Formaldehyde resin.Add epoxy resin in a kettle again and carry out reaction 0.5- at 60 DEG C or so
2h, reaction stop reaction after terminating.Persistently overheating dehydration, obtain laccol epoxy resin.It is subsequently added into acrylic monomers and disperses
Agent is stirred, and is put into agitator stirring, ultrasonic disperse after filtering with UV ink and appropriate amount of addition agent, ultrasonic 15min, is obtained after mixing
To raw lacquer ink.
Embodiment 3
In a kind of the raw lacquer ink and its modulator approach for digital spray printing and UV solidifications of the present embodiment, the matter of each component
It is as follows to measure percentage:
Ingredient names |
Mass percent(%) |
Laccol |
20 |
Formaldehyde |
6 |
Epoxy resin |
8 |
Polymerization inhibitor |
0.06 |
Dispersant |
0.06 |
Light trigger |
0.15 |
Ammoniacal liquor |
0.53 |
Dimethylbenzene |
20.2 |
UV ink |
40 |
Hexanediyl ester |
5 |
By above-mentioned mass ratio formula, the laccol select painted from safe and comfortable paint, flat interest paint, entrance of the city paint, hair dam paint, the Qinling Mountains or
One or more kinds of extractions of paint produced by other areas, decoct disk fraction more than 65%, and laccol content is more than 50%.
By above-mentioned mass ratio formula, by laccol solution and formaldehyde placing response kettle, enter in temperature control at 60 DEG C or so
Row reaction 0.5-1h, cross-linking reaction stop reaction after reaching requirement.Reaction terminates rear persistently overheating dehydration, and temperature reaches 136 DEG C
Left and right water purifies, and obtains Urushiol-Formaldehyde resin.Add epoxy resin in a kettle again and carry out reaction 0.5- at 60 DEG C or so
2h, reaction stop reaction after terminating.Persistently overheating dehydration, obtain laccol epoxy resin.It is subsequently added into acrylic monomers and disperses
Agent is stirred, and is put into agitator stirring, ultrasonic disperse after filtering with UV ink and appropriate amount of addition agent, ultrasonic 15min, is obtained after mixing
To raw lacquer ink.
A kind of technical performance of raw lacquer ink solidified for digital spray printing and UV prepared by above-described embodiment is referring to table 1.
The performance indications of table 1
Project |
Index |
The method of inspection |
Paint film appearance |
Brownish red |
|
Ink particle diameter |
Less than 5 μm |
Laser particle analyzer |
Solid content, % |
29% |
GB/T 1725-2007 |
UV cure times, s |
2-20 |
GB/T 6753.2 |
Viscosity,(Apply -4 glasss), s |
12-20 |
GB/T 1723 |
Surface tension, mN/m |
30-60 |
GB/T 22237 |
Freeze-thaw stability |
Surface tension and viscosity rate of change do not surpass 20% |
QB/T 2730.1 |
Bin stability |
Surface tension and viscosity rate of change do not surpass 20% |
QB/T 2730.1 |
Adhesive force, level |
1-2 |
GB/T 4893.4 |
Wearability |
4H |
GB/T 4893.8 |
Water resistance |
Paint film is intact |
GB/T 1733 |
It is resistance to sulfuric acid |
Paint film is intact |
GB/T 9274.1 |
Resistance to salt water(Sodium chloride) |
Paint film is intact |
GB/T 10834 |
Petrol-resistance |
Paint film is intact |
GB/T 1734 |