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CN100526400C - Ultraviolet cured printing ink composition and its uses - Google Patents

Ultraviolet cured printing ink composition and its uses Download PDF

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Publication number
CN100526400C
CN100526400C CN 200410102930 CN200410102930A CN100526400C CN 100526400 C CN100526400 C CN 100526400C CN 200410102930 CN200410102930 CN 200410102930 CN 200410102930 A CN200410102930 A CN 200410102930A CN 100526400 C CN100526400 C CN 100526400C
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methyl
acrylate
parts
ink composition
printing ink
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CN1800274A (en
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吴尉新
朱宝银
张宏
叶飞
张定德
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SHENZHEN PINEFIELD CHEMICAL ENTERPRISES CO Ltd
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SHENZHEN PINEFIELD CHEMICAL ENTERPRISES CO Ltd
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Abstract

本发明提供了一种可移印的紫外线固化油墨组合物，其含有至少一种聚氨酯型丙烯酸齐聚物、光聚合引发剂、活性稀释剂和任选的着色颜料、填料、流平剂、粘结剂，加工助剂等，该油墨组合物具有良好的紫外线固化性能、优秀的附着力、极强的耐磨性和优良的抗化学药品性能，可广泛用于要求耐磨和耐化学药品的电子产品和家用电器行业，如手机，电脑键盘，电话机，照相机，音响，DVD，MP3，电风扇，电吹风，多士炉，手表等。The present invention provides a pad printable ultraviolet curable ink composition, which contains at least one polyurethane type acrylic oligomer, a photopolymerization initiator, a reactive diluent and optionally colored pigments, fillers, leveling agents, adhesives Binders, processing aids, etc., the ink composition has good UV curing performance, excellent adhesion, strong wear resistance and excellent chemical resistance, and can be widely used in applications requiring wear resistance and chemical resistance Electronic products and household appliances industry, such as mobile phones, computer keyboards, telephones, cameras, audio, DVD, MP3, electric fans, hair dryers, toasters, watches, etc.

Description

Ultraviolet cured printing ink composition and application thereof
Invention field
The present invention relates to a kind of ultraviolet cured printing ink composition and application thereof, more particularly, relate to and contain at least a polyfunctional group urethane (methyl) acrylic ester oligomer and make base-material, but polyfunctional monomer is made the ink composite of bat printing of the light initiation polymerization of reactive thinner, and the application of said composition on products such as electronic product and household electrical appliance.
Background technology
As everyone knows, the printing of all kinds of signs on products such as electronic product and household electrical appliance, keyboard, button font etc., the method that adopts has usually: pad printer bat printing, silk screen printing, laser engraving and gilding technology.For the method for laser engraving, because equipment is expensive, production efficiency is low, and its production cost is higher, and is engraved structure, now exposes the ground color, only is suitable for the product of very little pattern.The gilding technology color is single, as golden, silver color, can not satisfy the requirement of the multiple color in market; And gilding technology requires the shape of workpiece more smooth, so bat printing or silk screen printing then are methods comparatively commonly used.The quality of printing quality and printing-ink are closely related in these class methods.In recent years, ultraviolet curing ink was owing to had that curing speed is fast, the mechanical and physical performance of filming is good and advantage such as environmental protection is little by little replacing traditional solvent type ink.
Now the main ingredient of disclosed ultraviolet curing ink generally includes epoxy acrylate, or urethane acrylate, or polyester acrylate etc.Wherein epoxy acrylate is comparatively superior at aspects such as thermotolerance, chemicals-resistant corrodibility, hardness and ultraviolet rate of initiation reactions, but film crisp, snappiness is not high, wear resistance is relatively poor; Urethane acrylate is then comparatively outstanding at aspects such as hardness, snappiness, wear resistant and tacks; With respect to epoxy acrylate, the polyester acrylate snappiness, good weatherability, but solidification rate is low, because of its viscosity is lower usually, and usually as epoxy acrylate, or the reactive thinner of urethane acrylate system.In recent years, the functional modification of polyester acrylate is accelerated, and increases functionality as the branched polyester acrylate, has improved solidification rate, has improved the cured film mechanical mechanics property.
At present product sold is to be applicable to screen printing ink basically on the open and market of patent documentation, it produces simple, construction requirement is not high, the prescription allotment is comparatively simple, disclose a kind of ultraviolet solidifiable ink for screen printing composition as U.S. Pat 4680368, its main ingredient comprises low-molecular weight compound of (a) urethane (methyl) acrylate, (b) free redical polymerization and (c) light polymerization initiator.German in addition Marabu company and Coates Screen company, U.S. Sun Chemical company, all there is this type of production marketing in Japanese JujoChemical company etc.But silk screen printing only adapts to than even curface, has defectives such as the little pattern of inexquisite, the difficult printing fine line bar of pattern, the production efficiency of printing are low.
And that pad printer bat printing construction has a cost is low, easy and simple to handle, the production efficiency height, and the character pattern fineness of printing off, effective is applicable to advantages such as irregular concave-convex curved surface or plane.In the manufacturing enterprise of electronic product and household electrical appliance, the pad printer bat printing has been important production technique at present, and pad printer has obtained general application.On electronic product and household electrical appliance, all kinds of signs, the button font of usual vehicle type ink printing are poor because of abrasion resistance, are fallen by friction easily in the use.In order to protect the bat printing pattern, most producers adopt the varnish Lacquer finish of wear-resisting wiping, and its detection for wear-resisting wiping at present requires to be generally anti-RCA more than 100 times.Because of spraying many one decks gloss oil, expense of raw materials and production cost rise on the one hand in the Lacquer finish protection.On the other hand, for automatic production, as present hand set machine shell coating process, after having sprayed middle coating intermediate, need workpiece is unloaded from automatic production line, the bat printing solvent type ink is installed onto workpiece the gloss oil that covers spray polyurethane lacquer or ultraviolet curing on the automatic spraying coating line again.This production efficiency is low, and the loading and unloading repeatedly of workpiece unavoidably have scratch or bump flower, is stained with sticking dust etc., causes very high fraction defective.In addition, usual vehicle type printing ink solvent content height, solvent evaporates influences operator ' s health, contaminate environment etc.
Japanese Patent JP2985536B2 discloses a kind of pad-transfer printing ink prescription of ultraviolet curing, comprises coloured material (anthraquinone class red pigment), base-material (polyurethane acrylate resin and silicon acrylic resin) and auxiliary agent (siloxanes flow agent, siloxanes coupler etc.).The bat printing of ultraviolet curing printing ink is crossed colloidality as can be known from the specification sheets of patent, better performances such as short period of time solidified nature and multicolor overprint, but its abrasion resistance does not then reach the requirement of present electronic product and household electrical appliance.
Therefore be starved of provide a kind of and have no irritating odor, nontoxic, non-corrosive ink composite, this ink composite has good ultraviolet curing performance, excellent sticking power, high wear resistance and good anti chemical properties, bat printing continuously, it is complete to cross glue, clear patterns.In product application such as electronic product and household electrical appliance, make the direct bat printing of printing ink in the ground of various complexity or painted surface, enhance productivity and good article rate, satisfy the requirement of electronic product and household electrical appliance.
Summary of the invention
It is quick to the invention provides a kind of curing, has excellent adhesive attraction, the ultraviolet curing pad-transfer printing ink of high wear resistance and anti chemical properties, be widely used in and require wear-resisting and chemical resistant electronic product and household electrical appliance, as mobile phone, computor-keyboard, telephone set, photographic camera, sound equipment, DVD, MP3, electric fan, hair dryer, toaster, wrist-watch etc.
But bat printing ultraviolet cured printing ink composition of the present invention, it contains following component and parts by weight:
(1) at least a urethane (methyl) acrylic ester oligomer: 20-90;
(2) Photoepolymerizationinitiater initiater: 1-15;
(3) reactive thinner: 10-85;
Described urethane (methyl) acrylic ester oligomer contains four (methyl) acrylate-functional groups at least, preferably contains the oligopolymer of six (methyl) acrylate-functional groups.
Described urethane (methyl) acrylic ester oligomer can obtain isocyanate terminated prepolymer by the prepolymer and the isocyanate reaction of terminal hydroxy group, and (methyl) acrylate reactions of prepolymer and hydroxy-functional obtains thus again.
Hydroxyl terminated prepolymer is the oligopolymer dibasic alcohol, also can be hydroxyl polyester, hydroxy polyethers, hydroxyl polyacrylic ester or hydroxyl polyurethane, specifically as polyoxyethylene glycol, polypropylene glycol, poly-(1,4-butyleneglycol), PEP-101, polycaprolactone glycol etc.
Isocyanic ester can be with aromatic diisocyanate such as tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), m xylene diisocyanate (XDI); Or aliphatic diisocyanate such as isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4 '-dicyclohexyl methane diisocyanate (HMDI), trimethylammonium hexamethylene diisocyanate (TMDI), hexahydrotoluene vulcabond (HTDI); Or their derivative such as HDI biuret, HDI tripolymer or the like.
Hydroxy-functional (methyl) acrylate such as methacrylic acid-2-hydroxyl ethyl ester, vinylformic acid-2-hydroxyl ethyl ester, methacrylic acid-2-hydroxypropyl acrylate, vinylformic acid-2-hydroxypropyl acrylate, trimethylolpropane diacrylate, TriMethylolPropane(TMP) dimethacrylate, pentaerythritol diacrylate, dimethyl pentaerythritol acrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl etc.
The structural formula of described urethane (methyl) acrylic ester oligomer generally can be expressed as follows:
(CH 2＝CR 4CO) mR 3OCONHR 2NHCOOR 1OCONHR 2NHCOOR 3(COCR 4＝CH 2) n
M+n ≧ 4 wherein, m, n are at least 1;
R 1, R 2, R 3Be respectively the main chain in hydroxyl terminated prepolymer, isocyanic ester, hydroxy-functional (methyl) acrylate, R 4=H or CH 3Its average molecular weight range is from about 500 to 10,000.
Contain ammonia ester bond (-NH-CO-O-) in urethane of the present invention (methyl) acrylic ester oligomer.Film and to form acyclic and/or annular hydrogen bond by H atom on the ammonia ester bond and O atom between high-polymer molecular.Masterpiece time spent outside, hydrogen bond is separable and absorb external energy (every mole absorbs 20～25kJ).After removing, external force can form hydrogen bond again more again.So hydrogen bond splits and the reversible repetition of formation again, and making films has high degree of mechanical wear resistance and toughness; Ammonia ester bond also brings strong tack, good performances such as chemical-resistant, acid and alkali-resistance, high-low temperature resistant and moisture-proof heat for filming in addition.
(methyl) acrylate-functional groups that contains four or more in urethane of the present invention (methyl) acrylic ester oligomer, has rapid reaction, high cross-linking density can be provided, and making films has high degree of mechanical wear resistance and hardness, and has good chemical-resistant etc.When the functional group of urethane (methyl) acrylic ester oligomer is less than four, as urethane (methyl) acrylic ester oligomer for two functional groups or trifunctional, because of cross-linking density is low, wear resistant is relatively poor, does not reach the requirement of present electronic product and household electrical appliance.
Described urethane (methyl) acrylic ester oligomer average molecular weight range is from about 500 to 10,000, and when molecular-weight average was lower than 500, paint film was crisp firmly, and snappiness is very poor; When molecular-weight average greater than 10,000 o'clock, resin reaction is active to be reduced, though the good hardness of the snappiness of filming is low, weather resistance, wear resistant are poor, can not satisfy actual requirement.
Described urethane (methyl) acrylic ester oligomer occupies the weight fraction of 20-90 in the present invention usually, is preferably 25-70.
Described reactive thinner is for containing (methyl) acrylate monomer of three (methyl) acrylate-functional groups or their mixture at least, and is concrete as Viscoat 295, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, the ethoxyquin Viscoat 295, the third oxidation Viscoat 295, the glycerol propoxylate triacrylate, tetramethylol methane tetraacrylate, two trimethylolpropane tetra-acrylate that contract, the ethoxyquin tetramethylol methane tetraacrylate, the third oxidation tetramethylol methane tetraacrylate, dipentaerythrityl ether five acrylate, dipentaerythrityl ether six acrylate or the like.It is low that described polyfunctional group (methyl) acrylate monomer has volatility usually, and laser curing velocity is fast, and the cured product cross-linking density is big, hardness height, characteristics such as chemical resistant properties is good, and the high and wear resistant of scratch resistance is good.If adopt simple function group or two functional groups (methyl) acrylate monomer as main reactive thinner, then will reduce the cross-linking density of whole prescription, wear resistant there is tangible reduction.In actual applications, viscosity is higher for adopting, and the ink formulations of the polyfunctional monomer that dilution capacity is low slightly can add a small amount of organic solvent in addition and adjust viscosity, so just can not be to the cured product cross-linking density, hardness, chemical resistant properties and wear resistant etc. is brought negative influence.Described organic solvent can be selected ester class, alcohols, ketone, pure ethers or their mixture for use.
Described reactive thinner is mainly used to control viscosity in the present invention, and its consumption is main to be decided according to the viscosity of prescription, and its part by weight scope generally is at 10-85, is preferably 10-60.
In ink composite of the present invention, light trigger is one of necessary component of uv-light polymerization curing reaction.Can adopt the light trigger of disclosed routine in the prior art.But well-known, the completely solidified problem of adding the photocuring system of pigment is a difficult problem always.Because the pigment in the printing ink has intensive to absorb and reflex action to UV-light, light trigger is the initiator of bottom particularly, is difficult to absorb sufficient UV-light.Cause curing reaction in order to make initiator can decomposite enough active substances, can increase initiator concentration, but this is effective to surface coating material.Because the top layer initiator absorbs UV-light in a large number, the UV-light that arrives the bottom still less, the more difficult curing in bottom.Therefore the colored paint that is added with pigment solidifies in order to make the bottom, must reduce the concentration of light trigger, therefore need do strict optimization for the two contradiction of balance to the concentration of light trigger.For the formula system of urethane (methyl) acrylate, behind the rete photocuring, because of the reason of oxygen inhibition, it is incomplete surface cure usually to occur, and promptly bottom solidifies substantially, and the surface is not dry and comfortable, easily produce fingerprint, even the surface becomes bad phenomenon such as mucus shape.Therefore; by existing light trigger is screened; ink composite of the present invention preferably adopts a kind of compound initiator system, promptly is suitable for the efficient acylphosphine oxide photoinitiator of deeply-curing and the mixture of the efficient solidified α in shallow top layer-hydroxyketone photoinitiator.More preferably its addition and blending ratio are controlled, to reach the completely solidified that causes top layer and bottom.
The acylphosphine oxide photoinitiator is as 2; 4; 6-Three methyl Benzene formyl diethyl phosphonate; 2; 4; 6-trimethylbenzoyl-oxyethyl group-phenyl phosphine oxide; 2; 4; 6-Three methyl Benzene formyl diphenyl phosphine oxide; two (2; 4; 6-trimethylbenzoyl)-phenyl phosphine oxide; two (2; 6-dimethoxy benzoyl)-(4 ', 4 '-dimethyl octyl group-2) Irgacure 1700 of phosphine oxide etc. and derived product such as CibaSpecialty Chemicals company; Irgacure 1800; Irgacure 1850; Irgacure2020; Irgacure 2010; Irgacure 2005; Irgacure 4265 etc.
α-hydroxyketone photoinitiator is as Irgacure 500, the Irgacure 1000 etc. of 1-hydroxycyclohexylphenylketone, 2-hydroxyl-2-methyl-1-phenyl-acetone-1,4-(2-hydroxyl ethoxy) phenyl-2-hydroxyl-2-acetone etc. and derived product such as Ciba Specialty Chemicals company.
Acylphosphine oxide photoinitiator and α-the two mixing of hydroxyketone photoinitiator, preferred part by weight is 1～10: between 10, the gross weight mark that this initiator system occupies in the ink combination composition formula is generally 1-15, is preferably 2-10.
Embodiment preferred of the present invention is the mixture of two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxides and 1-hydroxycyclohexylphenylketone.
Wherein, two (2; 4; 6-trimethylbenzoyl)-phenyl phosphine oxide can adopt the product I rgacure 819 of Ciba SpecialtyChemicals company; it has intensive to absorb at 370nm long wave place; for the prescription that contains pigment, even the relatively poor high-carbon black pigment system of light transmission, long wave can reach darker bottom.And Irgacure 819 is by phosphine formyl radical and phosphine methyl free radicals that Norrish I type photolysis produces, has highly vivaciously, the characteristics of autohemagglutination not, after cracking, promptly participates in oligopolymer and monomeric initiated polymerization.When the system that contains pigment is subjected to uviolizing, in layer participates in reaction from table to the Irgacure 819 of lining, so the Irgacure 819 of high efficiency of initiation is suitable for containing the deeply-curing of the thick coating of pigment.In addition, Irgacure 819 not flavescence have bleaching action, therefore also are suitable for white system formulation.Simultaneously, Irgacure 819 good heat stabilities are heated to 180 ℃ of no chemical reactions excellent storage stability take place.
Wherein, 1-hydroxycyclohexylphenylketone can adopt the product I rgacure 184 of Ciba Specialty Chemicals company.It has not xanthochromia, shallow efficiently top layer curing performance, and characteristics such as low volatility and shelf-stable are suitable for comprising the initiated polymerization of all colours prescription of varnish.
Two (2; 4; 6-trimethylbenzoyl)-mixture of phenyl phosphine oxide and 1-hydroxycyclohexylphenylketone in the shared part by weight of common 1-hydroxycyclohexylphenylketone should be higher than two (2; 4; 6-trimethylbenzoyl)-phenyl phosphine oxide; the preferred blending ratio of the two is 1～10: between 10, the gross weight mark that this initiator system occupies in the ink combination composition formula is generally 1-15, is preferably 2-10.
On the basis of above-mentioned main ingredient, also can contain components more well known in the art in the ink composite of the present invention, as tinting pigment, filler, pigment dispersing agent, flow agent, defoamer, adhesion promoter, matting agent etc., its associated viscera can be referring to US4680368, US4608409 and JP2985536 etc.
Specific embodiment of the present invention is: adopting as Japanese Patent JP2985536B2 when disclosed type siloxane flow agent realizes that bat printing is crossed outside the glue, also improve bat printing and cross the colloidality energy by the interpolation pearl filler, prevent pattern unedged (be commonly called as wire drawing or play silk) in the bat printing process, make the bat printing clear patterns complete, reach and cause better quick bat printing and cross the colloidality energy, realize the quick continuous production on the production line, enhance productivity etc.In addition, can preferably adopt the lime carbonate through fatty acid treatment, described lipid acid such as lauric acid, stearic acid or other lipid acid and composition thereof etc. form multi-level molecular layer coating on the lime carbonate surface, can obtain good dispersing property.
Described pearl filler occupies the weight fraction of 0-50 in ink composite of the present invention.
With each component in the ink composite of the present invention, at room temperature mix according to a certain percentage, it is qualified to be ground to fineness, can obtain corresponding printing ink.
The main physico-chemical parameter of ink composite of the present invention is as follows:
Fineness:＜20 microns;
Viscosity: 128～141KU (25 ℃);
VOC content: 0～100g/L.
It is worthy of note, ink composite of the present invention adopts black, white, red, yellow, blue, green etc. the of all kinds inorganic or pigment dyestuff of different this area routines to can be formulated into ink formulations of all kinds, adopt the common uv lamp of emmission spectrum, all obtain good curing performance in 200-400nm scope.The present invention's ink formulations of all kinds all have can be fast bat printing continuously, it is complete to cross glue, the characteristics of clear patterns; Has curing performance fast, outstanding sticking power, high abrasion resistance and anti chemical properties etc.Simultaneously; organic solvent content in the ink formulations is low; it is healthy to help the operator; help environment protection; be specially adapted to require abrasion performance and industries such as chemical resistant electronic product and household electrical appliance, as mobile phone, computor-keyboard, telephone set, photographic camera, sound equipment, DVD, MP3, electric fan, hair dryer, toaster, wrist-watch etc.
In actual applications, the ground that ink composite of the present invention is suitable for is very extensive, for example can select plastic cement such as ABS, PC, ABS/PC, PP, TPU, PVC for use, and all kinds of plastic cement of having primed, metal, alloy etc.
Comparatively preferred scheme of ink composite of the present invention in actual applications is to contain following component and parts by weight:
(1) at least a four or four above functional polyurethane (methyl) acrylic ester oligomers: 20-90, be preferably 25-70;
(2) Photoepolymerizationinitiater initiater: 1-15, be preferably 2-10;
(3) contain (methyl) acrylate monomer of trifunctional at least: 10-85, be preferably 10-60;
(4) surface tension auxiliary agent: 0.1-2.0, be preferably polyether-modified polydimethyl silica;
(5) lime carbonate: 0-50, be preferably 5-30;
(6) dispersion agent: 0-10
(7) optional colorant: 0-80.
According to above-mentioned preferred version, when tinting material is white pigment, can further preferred ink combination composition formula be: four or four above functional polyurethane (methyl) acrylate: dispersion agent: titanium dioxide: surface treated lime carbonate: three or three above functional group (methyl) acrylate monomers: polyether-modified polydimethylsiloxane: Irgacure 819:Irgacure 184=25-90: 0-5.0: 15-45: 5-30: 10-60: 0.1-2.0: 0.1-3: 1-5.
According to above-mentioned preferred version, when tinting material is high-carbon black pigment, can be mixed with black ink, its ratio of components is: four or four above functional polyurethane (methyl) acrylate: dispersion agent: high-carbon black pigment: surface treated lime carbonate: three or three above functional group (methyl) acrylate monomers: polyether-modified polydimethylsiloxane: Irgacure 819:Irgacure 184=25-90: 1-10: 0.1-15: 5-30: 10-60: 0.1-2.0: 0.2-5: 1-10.
According to above-mentioned preferred version, when tinting material is organic red, organic yellow during organic phthalocyanine etc., can be mixed with printing ink such as red, Huang, indigo plant, green.Its ratio of components is: four or four above functional polyurethane (methyl) acrylate: dispersion agent: tinting material is (organic red, organic yellow, or organic phthalocyanine): surface treated lime carbonate: three or three above functional group (methyl) acrylate monomers: polyether-modified polydimethylsiloxane: Irgacure 819:Irgacure 184=25-90: 1-10: 1-30: 5-30: 10-60: 0.1-2.0: 0.2-5: 1-10.
Embodiment
The following examples and reference examples are to be used for illustrating further the present invention, are not to be used for limiting the scope of the invention.
Abbreviation in embodiment and the reference examples has following meanings:
Disperbyk 163 contains the high-molecular block copolymer BYK Chemie company product of affine pigment group
819 pairs of (2,4,6-trimethylbenzoyl)-phenyl phosphine oxides of Irgacure
Ciba SpecialtyChemicals company product
Irgacure 184 1-hydroxycyclohexylphenylketone Ciba Specialty Chemicals company product
HDDA 1,6-hexanediyl ester
The TMPTA Viscoat 295
The PETTA tetramethylol methane tetraacrylate
Two aliphatic urethane acrylate UCB. S.A. (BE) Bruxelles Belgium of functional group products of Ebecryl 284 12%HDDA dilution
Trifunctional aliphatic urethane acrylate UCB. S.A. (BE) Bruxelles Belgium product of Ebecryl 264 15%HDDA dilution
NK-Oligo U-4HA four-functional group urethane acrylate Shin-nakamura Chemical company product
CN997 six functional groups aromatic urethane acrylate Sartomer company product
CN2282 four-functional group polyester acrylate Sartomer company product
Ebecryl 830 six functional groups polyester acrylate UCB. S.A. (BE) Bruxelles Belgium products
Embodiment 1
37.0 parts of six functional groups aromatic urethane acrylic ester oligomer CN997
163 1.5 parts of dispersion agent Disperbyk
30.0 parts of titanium dioxides
10.0 parts in surface treated lime carbonate
16.0 parts of TMPTA
0.2 part of polyether-modified polydimethylsiloxane
2.0 parts of Irgacure819
4.0 parts of Irgacure184
Printing ink manufacture technology: with each component in the foregoing description, by described mixed, be ground to fineness＜20 micron, promptly obtain corresponding printing ink.
Parameters of construction technology: the ground that is used for evaluation experimental is the polycarbonate plate of standard (thickness 2.0mm), the ground pre-treatment is cleaned with neutral cleaning agent, adopt small-sized pad printer (trade(brand)name: KIPP100 pad printer, the firm and persistent company in Hong Kong produces), the rectangle metal sheet of wide 15mm, long 35mm, etch depth 20um, bat printing glue head pressure 6kg/cm 2Ink viscosity is 1200cps, and ink film thickness is 8um.
The ink solidification condition: with earlier pre-roasting 60 ℃/3 minutes of workpiece, after the high pressure mercury vapour lamp of output rating 120W/cm, lamp was apart from about 15cm, 3 meters/minute of line speeds, irradiation time: 4～5 seconds.
Testing method or reference standard:
Sequence number Test item Method or reference standard
1 Curing depth The printing ink blade coating on 0-100 micron Hegman grind gage, is crossed the UV stove and exposed, film is peeled, the assessment curing depth.
2 Bat printing is crossed colloidality Bat printing hachure pattern, whether the thickness of observing lines with 40 times of magnifying glasses changes, whether wire drawing, horizontal infiltration; Bat printing large area pattern and steel plate reference area.
3 Sticking power GB9286,1 millimeter * 1 millimeter, 3M company 810 gummed papers.
4 Hardness GB1730, the UNI of Mitsubishi pencil, load 500g.
5 Anti-RCA ASTM Designation:F2357-04, the Norman Tool RCA of company wear resistant instrument, load 175g, continous way.This standard is that the effect of its abrasion is not differentiated in the paper tape of oiling and sample friction back to scrolling RCA wear resistant instrument under certain turnover number.
6 Alcohol resistance 1000g diameter 10mm circle copper rod wraps 4 layers of calico, soaks 99.5% alcohol, friction back and forth, and 1 second/time is back and forth.
7 Anti-MEK Drip 1-2 and drip MEK in film coated surface, keep moistening 2,5,15min after, do with air-blowing, it is not unusual to check that film coated surface has, gloss has or not considerable change.
8 Acid resistance Soak the PH=1.4 lactic acid solution, place 60 ℃, in the 90% humidity climatic chamber, 48 hours, checking films had or not variable color, cracking etc.
9 Alkali resistance Soak the PH=8.8 sodium hydrogen carbonate solution, place 60 ℃, in the 90% humidity climatic chamber, 48 hours, checking films had or not variable color, cracking etc.
10 High thermal resistance 80 ℃ of thermostat containers, 240 hours, checking films had or not cracking etc., detects sticking power.
11 Lower temperature resistance -20 ℃ of thermostat containers, 240 hours, checking films had or not cracking etc.
12 Humidity resistance 55 ℃, the damp and hot case of 100% humidity, 48 hours, checking films had or not cracking etc., detects sticking power.
13 Cold-resistant hot alternation performance → 70 ℃ of (40 ℃, 1 hour → 80 ℃, 1 hour) 48 circulations, 90% humidity, 48 hours, checking films had or not cracking etc., detects hardness, sticking power, anti-RCA.
Embodiment 2
50.0 parts of six functional groups aromatic urethane acrylic ester oligomer CN997
163 5.0 parts of dispersion agent Disperbyk
5.0 parts of high-carbon black pigments
12.0 parts in surface treated lime carbonate
23.0 parts of TMPTA
0.2 part of polyether-modified polydimethylsiloxane
819 3.0 parts of Irgacure
184 4.0 parts of Irgacure
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, testing method and reference standard are with embodiment 1.
Embodiment 3
50.0 parts of six functional groups aromatic urethane acrylic ester oligomer CN997
163 1.5 parts of dispersion agent Disperbyk
10.0 parts of the organic red pigment of naphthols
10.0 parts in surface treated lime carbonate
23.0 parts of TMTTA
0.2 part of polyether-modified polydimethylsiloxane
2.0 parts of Irgacure819
4.0 parts of Irgacure184
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, testing method and reference standard are with embodiment 1.
Embodiment 4
50.0 parts of six functional groups aromatic urethane acrylic ester oligomer CN997
2.0 parts of dispersion agent Disperbyk163
12.0 parts of the organic yellow ultramarines of virtue acid amides
10.0 parts in surface treated lime carbonate
20.0 parts of TMPTA
0.2 part of polyether-modified polydimethylsiloxane
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, testing method and reference standard are with embodiment 1.
Embodiment 5
50.0 parts of six functional groups aromatic urethane acrylic ester oligomer CN997
163 1.5 parts of dispersion agent Disperbyk
10.0 parts of phthalocyanine blues
10.0 parts in surface treated lime carbonate
23.0 parts of TMPTA
0.2 part of polyether-modified polydimethylsiloxane
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, testing method and reference standard are with embodiment 1.
Embodiment 6
50.0 parts of six functional groups aromatic urethane acrylic ester oligomer CN997
163 1.5 parts of dispersion agent Disperbyk
10.0 parts of phthalocyanine greens
10.0 parts in surface treated lime carbonate
23.0 parts of TMPTA
0.2 part of polyether-modified polydimethylsiloxane
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, testing method and reference standard are with embodiment 1.
Embodiment 7
37.0 parts of four-functional group polyurethane acrylic ester oligomer NK-Oligo U-4HA
163 1.5 parts of dispersion agent Disperbyk
30.0 parts of titanium dioxides
10.0 parts in surface treated lime carbonate
16.0 parts of TMPTA
0.2 part of polyether-modified polydimethylsiloxane
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
This embodiment is on embodiment 1 basis, only uses the four-functional group polyurethane acrylic ester oligomer to replace hexafunctional aliphatic urethane acrylates oligopolymer at 1: 1, and other components and ratio remain unchanged.
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, testing method and reference standard are with embodiment 1.
Reference examples 1
264 43.5 parts of trifunctional aliphatic urethane acrylate oligopolymer Ebecryl
163 1.5 parts of dispersion agent Disperbyk
30.0 parts of titanium dioxides
10.0 parts in surface treated lime carbonate
9.5 parts of PETTA
0.2 part of polyether-modified polydimethylsiloxane
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
This reference examples is on embodiment 1 basis, press the oligopolymer amount 1: 1, replace the hexafunctional aliphatic urethane acrylates oligopolymer with trifunctional urethane acrylate Ebecryl 264, substitute TMPTA with PETTA simultaneously and make thinner, and their ratio adjusted, with the influence that two HDDA of functional group among the balance Ebecryl 264 bring, other components and ratio remain unchanged.
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, testing method and reference standard are with embodiment 1.
Reference examples 2
284 42.0 parts of the two aliphatic urethane acrylate oligopolymer Ebecryl of functional group
163 1.5 parts of dispersion agent Disperbyk
30.0 parts of titanium dioxides
11.0 parts in surface treated lime carbonate
16.0 parts of PETTA
0.2 part of polyether-modified polydimethylsiloxane
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
This reference examples is on embodiment 1 basis, press the oligopolymer amount 1: 1, replace the hexafunctional aliphatic urethane acrylates oligopolymer with trifunctional urethane acrylate Ebecryl 284, substitute TMPTA with PETTA simultaneously and make thinner, and their ratio adjusted, with the influence that two HDDA of functional group among the balance Ebecryl 284 bring, other components and ratio remain unchanged.
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, testing method and reference standard are with embodiment 1.
Reference examples 3
830 37.0 parts of six functional groups polyester acrylic ester oligomer Ebecryl
163 1.5 parts of dispersion agent Disperbyk
30.0 parts of titanium dioxides
10.0 parts in surface treated lime carbonate
16.0 parts of TMPTA
0.2 part of polyether-modified polydimethylsiloxane
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
This reference examples is on embodiment 1 basis, only uses six functional groups polyester acrylic ester oligomer to replace hexafunctional aliphatic urethane acrylates oligopolymer at 1: 1, and other components and ratio remain unchanged.
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, testing method and reference standard are with embodiment 1.
Reference examples 4
37.0 parts of four-functional group polyester acrylic ester oligomer CN2282
163 1.5 parts of dispersion agent Disperbyk
30.0 parts of titanium dioxides
10.0 parts in surface treated lime carbonate
16.0 parts of TMPTA
0.2 part of polyether-modified polydimethylsiloxane
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
This reference examples is on embodiment 1 basis, only uses four-functional group polyester acrylic ester oligomer to replace hexafunctional aliphatic urethane acrylates oligopolymer at 1: 1, and other components and ratio remain unchanged.
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, testing method and reference standard are with embodiment 1.
Reference examples 5
37.0 parts of six functional groups aromatic urethane acrylic ester oligomer CN997
163 1.5 parts of dispersion agent Disperbyk
30.0 parts of titanium dioxides
10.0 parts in surface treated lime carbonate
16.0 parts of HDDA
0.2 part of polyether-modified polydimethylsiloxane
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
This reference examples is on embodiment 1 basis, only replaces TMPTA with HDDA1:1, and other components and ratio remain unchanged.
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, testing method and reference standard are with embodiment 1.
Contrast test film performance result such as following table 1 and table 2:
Table 1
Sequence number Test item Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
1 Curing depth 100 microns 80 microns 100 microns 100 microns 100 microns 100 microns
2 Bat printing is crossed colloidality No wire drawing, no horizontal infiltration; It is complete to cross glue, clear patterns. No wire drawing, no horizontal infiltration; It is complete to cross glue, clear patterns. No wire drawing, no horizontal infiltration; It is complete to cross glue, clear patterns. No wire drawing, no horizontal infiltration; It is complete to cross glue, clear patterns. No wire drawing, no horizontal infiltration; It is complete to cross glue, clear patterns. No wire drawing, no horizontal infiltration; It is complete to cross glue, clear patterns.
3 Sticking power 0 grade 0 grade 0 grade 0 grade 0 grade 0 grade
4 Hardness 2H 2H 2H 2H 2H 2H
5 Anti-RCA 1000 not show-through looks 1000 not show-through looks 800 show-through looks 700 show-through looks 700 show-through looks 700 show-through looks
6 Alcohol resistance 500 not show-through looks 500 not show-through looks 500 not show-through looks 500 not show-through looks 500 not show-through looks 500 not show-through looks
7 Anti-MEK By By By By By By
8 Acid resistance By By By By By By
9 Alkali resistance By By By By By By
10 High thermal resistance By By By By By By
11 Lower temperature resistance By By By By By By
12 Humidity resistance By By By By By By
13 Cold-resistant hot alternation performance By By By By By By
Table 2
Sequence number Test item Embodiment 7 Reference examples 1 Reference examples 2 Reference examples 3 Reference examples 4 Reference examples 5
1 Curing depth 100 microns 100 microns 100 microns 100 microns 100 microns 100 microns
2 Bat printing is crossed colloidality No wire drawing, no horizontal infiltration; It is complete to cross glue, clear patterns. Slight wire drawing and horizontal infiltration are arranged; It is complete to cross glue, but pattern is clear inadequately. Slight wire drawing and horizontal infiltration are arranged; It is complete to cross glue, but pattern is clear inadequately. Slight wire drawing and horizontal infiltration are arranged; It is complete to cross glue, but pattern is clear inadequately. Slight wire drawing and horizontal infiltration are arranged; It is complete to cross glue, but pattern is clear inadequately. It is imperfect to cross glue.
3 Sticking power 0 grade 0 grade 0 grade 1 grade 5 grades 0 grade
4 Hardness H F F H H H
5 Anti-RCA 250 show-through looks 25 show-through looks 15 show-through looks 100 show-through looks 10 show-through looks 50 show-through looks
6 Alcohol resistance 230 show-through looks 45 show-through looks 45 show-through looks 450 show-through looks 190 show-through looks 500 show-through looks
7 Anti-MEK By / / / / /
8 Acid resistance By / / / / /
9 Alkali resistance By / / / / /
10 High thermal resistance By / / / / /
11 Lower temperature resistance By / / / / /
12 Humidity resistance By / / / / /
13 Cold-resistant hot alternation performance By / / / / /
Annotate: "/" represents that this Xiang Wei tests
Estimate: by embodiment and reference examples more as can be seen; the present invention by at least a four or the polyurethane acrylic ester oligomer of four above functional groups make base-material; three and three above functional group propenoic acid ester monomers are made reactive thinner; inorganic and/or pigment dyestuff is made tinting material; and the mixture of acylphosphine oxide and α-alcohol ketone photoinitiator formation; but the ink composite of the bat printing of ultraviolet-initiated polymerization has the high abrasion resistance of anti-RCA more than 200 times; has curing performance fast simultaneously; outstanding sticking power; high rigidity; acid and alkali-resistance; high-low temperature resistant; moisture-proof heat, characteristics such as chemical proof and environmental protection can satisfy the requirement of present electronic product and household electrical appliance.And it is lower to do the base-material abrasion resistance than the propenoic methyl carbamate oligopolymer of two functional groups of hanging down functionality and trifunctional, and the ethanol-tolerant performance is relatively poor, can not satisfy the requirement of present electronic product and household electrical appliance.As for the polyester acrylic ester oligomer of six and four-functional group of functional modification in recent years, still do not reach higher abrasion resistance as can be seen from the result of reference examples.Simultaneously, the acrylate monomer of simple function group and two functional groups is as main reactive thinner, and the wear resistant of prescription and bat printing are crossed colloidality can tangible influence.In addition, the present invention has improved bat printing and has crossed the colloidality energy by adding pearl filler, prevents wire drawing in the bat printing process, and the bat printing clear patterns is complete, reaches to cause better quick bat printing and cross colloidality, realizes the quick continuous production on the production line, has improved production efficiency etc.

Claims (13)

  1. But 1, a kind of ultraviolet cured printing ink composition of bat printing, it contains following component and parts by weight:
    (1) at least a urethane (methyl) acrylic ester oligomer: 20-90;
    (2) Photoepolymerizationinitiater initiater: 1-15;
    (3) reactive thinner: 10-85;
    Described urethane (methyl) acrylic ester oligomer contains four (methyl) acrylate-functional groups at least; described reactive thinner is the acrylate that contains three or three above hydroxy functional groups; described light trigger adopts the mixture of acylphosphine oxide photoinitiator and alpha-alcohol ketone photoinitiator, and wherein the part by weight of acylphosphine oxide photoinitiator and alpha-alcohol ketone photoinitiator is 1-10:10.
  2. 2, ultraviolet cured printing ink composition according to claim 1 is characterized in that the parts by weight of described photoinitiator mixtures in ink composite are 2-10.
  3. 3, ultraviolet cured printing ink composition according to claim 1, it is characterized in that described urethane (methyl) acrylic ester oligomer can obtain holding prepolymer with cyanate by the prepolymer of terminal hydroxy group and isocyanate reaction, (methyl) acrylate reactions of prepolymer and hydroxy-functional obtains thus again.
  4. 4, ultraviolet cured printing ink composition according to claim 1 is characterized in that described reactive thinner is selected from Viscoat 295, pentaerythritol triacrylate, the ethoxyquin Viscoat 295, the third oxidation Viscoat 295, the glycerol propoxylate triacrylate, tetramethylol methane tetraacrylate, two trimethylolpropane tetra-acrylate that contract, the ethoxyquin tetramethylol methane tetraacrylate, the third oxidation tetramethylol methane tetraacrylate, dipentaerythrityl ether five acrylate, dipentaerythrityl ether six acrylate or their mixture.
  5. 5, ultraviolet cured printing ink composition according to claim 1 is characterized in that described poly-
    The molecular-weight average of ammonia ester (methyl) acrylic ester oligomer is 500-10,000.
  6. 6, ultraviolet cured printing ink composition according to claim 1 is characterized in that also comprising in tinting pigment, filler, pigment dispersing agent, flow agent, defoamer, adhesion promoter and the matting agent one or more.
  7. 7, ultraviolet cured printing ink composition according to claim 1 is characterized in that also comprising pearl filler, flow agent, tinting pigment and pigment dispersing agent.
  8. But 8, a kind of ultraviolet cured printing ink composition of bat printing, it contains following component and parts by weight:
    (1) at least a four or four above functional polyurethane (methyl) acrylic ester oligomers:
    20—90；
    (2) Photoepolymerizationinitiater initiater: 1-15;
    (3) contain (methyl) acrylate monomer of trifunctional at least: 10-85;
    (4) surface tension auxiliary agent: 0.1-2.0;
    (5) lime carbonate: 0-50;
    (6) dispersion agent: 0-10;
    (7) optional colorant: 0-80;
    Described Photoepolymerizationinitiater initiater adopts the mixture of acylphosphine oxide photoinitiator and alpha-alcohol ketone photoinitiator.
  9. 9, ultraviolet cured printing ink composition according to claim 8 is characterized in that described ink composite contains following component and parts by weight: four or four above functional polyurethane (methyl) acrylate: dispersion agent: titanium dioxide: surface treated lime carbonate: three or three above functional group (methyl) acrylate monomers: polyether-modified polydimethylsiloxane: Irgacure819:Irgacure184=20-90:0-5.0:1-60:5-50:10-85:0.1-2.0:0.1-2.0:0.1-3:1-8.
  10. 10, the described ultraviolet cured printing ink composition of claim 8 when it is characterized in that described tinting material is high-carbon black pigment, can be mixed with black ink.
  11. 11, the described ink composite of claim 10 is characterized in that the ratio of components of black ink is: four or four above functional polyurethane (methyl) acrylate: dispersion agent: high-carbon black pigment: surface treated lime carbonate: three or three above functional group (methyl) acrylate monomers: polyether-modified polydimethylsiloxane: Irgacure819:Irgacure184=20-90:1-10:0.1-15:5-50:10-85:0.1-2.0:0.2-5:1-10.
  12. 12, the described ink composite of claim 8 is characterized in that described tinting material is organic red, organic yellow, when organic phthalein is blue or green, can be mixed with red, Huang, indigo plant, green ink.
  13. 13, the described ink composite of claim 12, four or four above functional polyurethane (methyl) acrylate: dispersion agent: tinting material: surface treated lime carbonate: three or three above functional group (methyl) acrylate monomers: polyether-modified polydimethylsiloxane: Irgacure819:Irgacure184=20-90:1-10:1-80:5-50:10-85:0.1-2 .0:0.2-5:1-10.
CN 200410102930 2004-12-31 2004-12-31 Ultraviolet cured printing ink composition and its uses Expired - Fee Related CN100526400C (en)

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