A kind of radiation-hardenable jetted ink and preparation method thereof
Technical field
The present invention relates to a kind of radiation-hardenable jetted ink and preparation method thereof; Especially relate to a kind of radiation-hardenable jetted ink and preparation method who is applied to the plastic material surface; This jetted ink can carry out air brushing at the plastic cement products outside surface through digit inkjet printer and print; Air brushing stamping ink layer directly uses as the top layer, no longer applies other coatings or resist.
Background technology
Ink jet printing is to penetrate the ink flow on stock through the computer control nozzle; Thereby obtain the mode of printing of writings and image; Ink jet printing need not contact, need not pressure, need not forme, only needs canned data in the robot calculator is input to ink-jet printer, i.e. the may command printing process.Ink jet printing also has the characteristic of variable information printing in addition.
Water-based and solvent-borne type jetted ink are present ink jet inks known and commonly used.Yet; It is tinting material that aqueous ink-jet inks generally adopts water-soluble dye, has problems such as water dungeon degree, light fastness difference, and its drying process of water color ink needs for a long time and energy simultaneously; Its ground of undertaking the printing of must be the adsorbable one type of material of water, and the ground that can not adsorb for water then can't be suitable for.The rate of drying of solvent type ink, water dungeon degree, light fastness, thermostability, oxidative stability etc. have been compared many good property with water color ink, but all there are problems such as toxicity, inflammableness in most of solvent, does not meet environmental requirement.In the 3C electron trade; Resistance, water tolerance, the ultraviolet resistance of printing ink and curing back China ink layer are had relatively high expectations according to property, wear resistance and other relevant environment testabilities; Water-based and solvent-borne type jetted ink can't reach the correlated performance requirement, generally need to apply other coatings or resist again at its jetted ink layer upper surface.
The radiation curable ink-jet printing technology is mainly reflected in high speed printing, environmental protection, chemical-resistant, wear resistance, light permanency and aspect such as the material scope of application widely as a kind of less energy-consumption, its significant advantage of free of contamination technology.Conventional at present UV jetted ink is used for plastic cement; Especially the plastic cement of crystallinity such as PP, PE, PET, low surface energy; Generally need carry out surface preparation to base material through methods such as flame, plasma etching or coronas; And after the UV jetted ink solidifies, do not have enough flexiblely meeting thick basement flexure or required extension when crooked, solidify the back ink lay and dropping hammer, be easy to generate when falling cracking or dropping thereby cause.
Summary of the invention
The objective of the invention is to overcome general water-based, solvent-borne type jetted ink over-all properties is relatively poor; Can not be as the direct applied shortcoming of plastic cement top layer printing ink; A kind of printing ink directly uses in the plastic cement products top layer and provide, and no longer applies radiation-hardenable jetted ink of other coatings or resist and preparation method thereof.
A kind of radiation-hardenable jetted ink comprises prepolymer, reactive monomer, pigment, light trigger, dispersion agent and other auxiliary agents, and its weight percentage is respectively:
Described prepolymer is one or more the miscellany in urethane acrylate, polyester acrylate, the hyperbranched polyester acrylic ester.
Described reactive monomer is one or more the miscellany in single functionality monomer, difunctionality monomer and three-functionality-degree or the polyfunctionality monomer.
The reactive monomer of described single functionality is selected from (methyl) vinylbenzene, vinyl pyrrolidone, vinyl-acetic ester, (methyl) propenoate, vinylformic acid (different) monooctyl ester, vinylformic acid (different) butyl ester, NSC 11786, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester, 2-phenoxyethyl acrylate, dodecylacrylate, iso-bornyl acrylate, ethoxy ethoxy ethyl propylene acid esters, THF propenoate, 2-hydroxyethyl (methyl) propenoate SULPHOSUCCINIC ACID ESTER, N; The miscellany of one or more in N-DMAA, acryloyl morpholine, N-butyl-1, the 2 acryloxy urethanum.
The reactive monomer of described difunctionality and polyfunctionality is selected from 1; The miscellany of one or more in 4-butylene glycol diacrylate, 1,6 hexanediol diacrylate, O-phthalic acid diethylene glycol diacrylate, neopentylglycol diacrylate, ethoxylated neopentylglycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, propoxylation Viscoat 295, ethoxylated trimethylolpropane triacrylate, Viscoat 295, pentaerythritol triacrylate, the cyclopentenyl isocyanuric acid triacrylate.
Described pigment is one or more the miscellany in phthalein cyanogen pigment, quinacridone pigment, azo pigment, benzimidazolone pigment, the charcoal blacks.
Described light trigger is selected from 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxyl-cyclohexyl benzophenone, 2-methyl isophthalic acid-(4-first sulfydryl phenyl)-2-morpholine-1-acetone, 2-benzyl-2; 2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 2; 2-dimethoxy-2-phenyl methyl phenyl ketone, 2; 4; 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester, phenyl two (2; 4,6-trimethylbenzoyl) miscellany of one or more in the aliphatic tertiary amine of phosphine oxide, UVNUL MS-40, Michler's keton, isopropyl thioxanthone, salt compounded of iodine light trigger, sulfonium salt photoinitiator initiator, iron arene light trigger, 4-dimethyl ethyl aminobenzoate, acroleic acid esterification.
Described hyper-dispersant is the hyper-dispersant that has anchor formula group and solvent chain.
The preparation method of said radiation-hardenable jetted ink comprises the steps:
1) part reactive monomer, prepolymer and hyper-dispersant are mixed and stir, make the hyper-dispersant dissolving and be evenly dispersed in the mixture of partial monosomy and prepolymer;
2) adding pigment is grinding, is stirring, is disperseing to grind the pigment dispersion color paste that obtains higher concentration on the multi-purpose machine;
3) add light trigger, other auxiliary agents, remaining activity monomer etc. again, and disperse with the ultra-sonic dispersion appearance;
4) with ultra-fine filter screen printing ink is filtered at last, can obtain radiation curable ink jet inks.
Radiation-hardenable jetted ink provided by the invention has good tack, wear resistance, chemical proofing and anti-environmental testing performance, can be used as 3C electron-like plastic cement products top layer printing ink and directly uses, and no longer applies other coatings or resist.
When radiation-hardenable jetted ink provided by the invention directly used as top layer printing ink, its China ink layer performance satisfied the correlated performance test of 3C electronic product.
Embodiment:
For more detailed explanation summary of the invention of the present invention, further specify below in conjunction with specific embodiment.
Embodiment 1
Weight percentage is respectively:
Part reactive monomer, prepolymer and hyper-dispersant are mixed and stir, make the hyper-dispersant dissolving and be evenly dispersed in the mixture of partial monosomy and prepolymer; Adding pigment is grinding, is stirring, is disperseing to grind the pigment dispersion color paste that obtains higher concentration on the multi-purpose machine; Add light trigger, other auxiliary agents, remaining activity monomer etc. again, and disperse with the ultra-sonic dispersion appearance; With ultra-fine filter screen printing ink is filtered at last, can obtain radiation curable ink jet inks.
Process of lapping uses is that the SDF-400 of dragon Xinghua, Shandong construction machinery Group Co.,Ltd grinds, stirs, disperses multi-purpose machine, and milling time is 2~20 hours, is stirred under 7000 rev/mins the rotating speed to carry out; Dispersion process is to analyse the DS-2510DTH ultra-sonic dispersion appearance that ultrasonic instrument ltd produces with the Shanghai life, and jitter time is 30~60 minutes.Pigment red 122 belongs to quinacridone pigment, and dispersion agent SOLSPERSE 32000 is produced by U.S. Lu Borun petrochemical corporation (complex).Test result is seen table 2.
Embodiment 2
Radiation-hardenable jetted ink weight percentage is respectively:
Through making the radiation-hardenable jetted ink with embodiment 1 same preparation method, test result is seen table 2.
Case study on implementation 3-5 sees table 1, can make the radiation-hardenable jetted ink of cyan, yellow and black, and the preparation method is with embodiment 1.
The embodiment 3-example 5 of table 1 cyan, yellow and black
Wherein, said pigment particle size is 0.02~1 μ m, preferred 0.1-0.7 μ m, more preferably 0.2-0.5 μ m.The viscosity of radiation-hardenable jetted ink is 10~50mPas, and its surface tension is 20~50dynes/cm.
Table 2 is the test result of embodiment 1~5:
The test result of table 2. embodiment 1~5
In the above-mentioned test:
1. viscosity test adopts NDJ-8S digital display rotary viscosity measuring.
2. the OCA15EC video optics contact angle measurement test of the German Dataphysics of surface tension test employing company.
3. anti-makeup test: sunscreen is applied on the specimen China ink layer with writing brush; Normal temperature is placed and to be gone to after 10 minutes in temperature is that 80 ℃, humidity are that 80% constant temperature and humidity machine is placed; After 24 hours test sample is taken out; Wash sunscreen off, dry, normal temperature places after 4 hours, on sample China ink layer, draws the chess lattice with the 2mm spacing, the vertical direction brute force is drawn 1 time after pasting with the test gummed paper again.
4. the test of anti-damping fluid: the buffered soln of putting into pH=4.6 to specimen is placed after 48 hours and is taken out, and washes, dries, normal temperature places after 4 hours, on sample China ink layer, draws the chess lattice with the 2mm spacing, and the vertical direction brute force is drawn 1 time after pasting with the test gummed paper again.
5. hundred lattice test: on sample China ink layer, draw the chess lattice with icking tool earlier, paste back vertical direction brute force with the test gummed paper again and draw 3 times, obscission can not be arranged with 1mm spacing intersection.
6.RCA wear-resisting test: specimen is positioned on the RCA wear testing machine; On paper tape, apply 275g gravity; Paper tape comes and goes/minute speed commute friction sample China ink layer with 33 times; Rubbing comes and goes back samples China ink layer for 30 times and can not have and come off or the heavy wear phenomenon, can not expose the base material of China ink layer lower floor.
7. resistance test: specimen is positioned on the trier; Periodically adding alcohol makes it keep humidity; Apply under the 500g gravity condition with 40 times at the test eraser and to come and go/minute speed commutes friction sample China ink layer, rub comes and goes back samples China ink for 250 times and layer can not have and to come off or the heavy wear phenomenon.
8. brine spray test: putting into temperature to specimen is 35 ℃, the brine spray experimental machine of the environment of 5%NaCl; Place take out after 72 hours, wash, dry, normal temperature places after 4 hours; On sample China ink layer, draw the chess lattice, paste back vertical direction brute force with the test gummed paper again and draw 1 time with the 2mm spacing.
9. ultraviolet ray test: after half of specimen sheet covered with black belt; Place placement taking-up after 72 hours in 20cm position under the ultraviolet test lamp to the specimen sheet; Normal temperature was placed after 4 hours; On sample China ink layer, draw the chess lattice, paste back vertical direction brute force with the test gummed paper again and draw 1 time with the 2mm spacing.
10. thermal shock test: put into the thermal shock experiment machine to specimen; Controlled temperature is-40 ℃ and places after 2 hours; Controlled temperature is 85 ℃ to be placed 2 hours, placed so repeatedly after 72 hours and took out, and normal temperature was placed after 4 hours; On sample China ink layer, draw the chess lattice, paste back vertical direction brute force with the test gummed paper again and draw 1 time with the 2mm spacing.
The test 11. drop hammer: with 500G weight steel ball from 50CM height free-falling impact test sample China ink layer 6 times.
12. pencil hardness test: with the board U NIF of Mitsubishi type pencil, loading 1000g counterweight, pencil-lead becomes 45 with the ink film face, and pencil-lead comes and goes 5 times and comes and goes miles of relative movement at every turn on ink film is 10mm.
Determinating reference:
1), before the experiment/back specimen China ink layer can not have fade, variable color, be full of cracks, bubble, come off, the scarce limit of distortion etc. and referred to give as security the scratch phenomenon;
2), gummed paper is pasted back specimen China ink layer can not have drop (lacking limit: when 2/3 above area of chess lattice drops).