CN1800274A - Ultraviolet cured printing ink composition and its uses - Google Patents
Ultraviolet cured printing ink composition and its uses Download PDFInfo
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- CN1800274A CN1800274A CN 200410102930 CN200410102930A CN1800274A CN 1800274 A CN1800274 A CN 1800274A CN 200410102930 CN200410102930 CN 200410102930 CN 200410102930 A CN200410102930 A CN 200410102930A CN 1800274 A CN1800274 A CN 1800274A
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Abstract
The invention provides a bat printing ultraviolet ray curing printing ink composition which at least comprises a polyurethanes acrylic oligomer, a light polymerization initiator, an active diluents and the optional painting agent, pad, leveling agent, catalytic agent and grip auxiliary.
Description
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 polyurethane (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 diluent, and the application of said composition on the products such as electronic product and household electrical appliance.
Background technology
As everyone knows, the printing of all kinds of signs on the products such as electronic product and household electrical appliance, keyboard, button font etc., the method that usually adopts has: pad printer bat printing, serigraphy, 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, such as golden, silver color, and requirement that can not the satisfying the market multiple color; And gilding technology requires the shape matching of workpiece smooth, so bat printing or serigraphy then are the methods of comparatively commonly using. 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 rate is fast, the mechanical and physical performance of filming is good and the advantage such as environmental protection is little by little replacing traditional solvent type ink.
The key component of existing published ultraviolet curing ink generally includes epoxy acrylate, or urethane acrylate, or polyester acrylate etc. Wherein epoxy acrylate is comparatively superior at aspects such as heat resistance, chemicals-resistant corrosivity, hardness and ultraviolet rate of initiation reactions, but film crisp, pliability is not high, wearability is relatively poor; Urethane acrylate is then comparatively outstanding at aspects such as hardness, pliability, abrasion performance and tacks; With respect to epoxy acrylate, the polyester acrylate pliability, good weatherability, but solidification rate is low, because its viscosity is lower usually, and usually as epoxy acrylate, or the reactive diluent of urethane acrylate system. In recent years, the functional modification of polyester acrylate is accelerated, and increases degree of functionality such 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 such as US Patent No. 4680368, its key component comprises the low molecular weight compound of (a) polyurethane (methyl) acrylate, (b) free redical polymerization and (c) light polymerization initiator. In addition German Marabu company and Coates Screen company, U.S. Sun Chemical company, all there is this type of production marketing in Japanese Jujo Chemical company etc. But serigraphy only adapts to than even curface, has the 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, and production efficiency is high, and the character pattern that prints off is exquisite, effective, is applicable to the 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 technology 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 procedure. In order to protect the bat printing pattern, most producers adopt the varnish Lacquer finish of wear-resisting wiping, and its testing requirement for wear-resisting wiping is generally anti-RCA more than 100 times at present. Because 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 automated production, such as present hand set machine shell coating process, after having sprayed middle coating intermediate, need workpiece is unloaded from automatic assembly line, the bat printing solvent type ink is installed onto workpiece the gloss oil that automatic coating line upper cover is sprayed polyurethane lacquer or ultraviolet curing again. This production efficiency is low, and the repeatedly loading and unloading of workpiece unavoidably have scratch or bump flower, stick dust etc., cause very high defect rate. In addition, usual vehicle type printing ink solvent content is high, and solvent evaporates affects operator ' s health, contaminated environment etc.
Japan Patent JP2985536B2 discloses a kind of pad-transfer printing ink prescription of ultraviolet-curing, comprises coloured material (Anthraquinones red pigment), base-material (polyurethane acrylate resin and silica acrylic acid resin) and auxiliary agent (siloxanes levelling agent, siloxanes coupling agent etc.). The bat printing of ultraviolet-curing printing ink is crossed colloidality as can be known from the specification of patent, the better performances such as short time curing property 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 adhesive force, high wearability and good anti chemical properties, continuous bat printing, it is complete to cross glue, clear patterns. In the products such as electronic product and household electrical appliance are used, make the direct bat printing of printing ink in the ground of various complexity or painted surface, enhance productivity and yields, 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 wearability and anti chemical properties, be widely used in and require wear-resisting and chemical resistant electronic product and household electrical appliance, such as mobile phone, computor-keyboard, telephone set, 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 polyurethane (methyl) acrylic ester oligomer: 20-90;
(2) Photoepolymerizationinitiater initiater: 1-15;
(3) reactive diluent: 10-85;
Described polyurethane (methyl) acrylic ester oligomer contains four (methyl) acrylate-functional groups at least, preferably contains the oligomer of six (methyl) acrylate-functional groups.
Described polyurethane (methyl) acrylic ester oligomer can obtain isocyanate terminated prepolymer by 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 oligomer dihydroxylic alcohols, also can be hydroxyl polyester, hydroxy polyethers, hydroxyl polyacrylate or hydroxyl polyurethane, specifically such as polyethylene glycol, polypropylene glycol, poly-(BDO), PEP-101, polycaprolactone glycol etc.
Isocyanates can be with aromatic diisocyanate such as toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), m xylene diisocyanate (XDI); Or aliphatic diisocyanate such as IPDI (IPDI), hexamethylene diisocyanate (HDI), HMDI (HMDI), trimethyl hexamethylene diisocyanate (TMDI), hexahydrotoluene vulcabond (HTDI); Or their derivative such as HDI biuret, HDI tripolymer etc.
Hydroxy-functional (methyl) acrylate such as 2-hydroxyethyl methacry-late, acrylic acid-2-hydroxyl ethyl ester, methacrylic acid-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, trimethylolpropane diacrylate, trimethylolpropane dimethylacrylate, pentaerythritol diacrylate, dimethyl pentaerythritol acrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl etc.
The structural formula of described polyurethane (methyl) acrylic ester oligomer generally can be expressed as follows: (CH2＝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, isocyanates, hydroxy-functional (methyl) acrylate, R4=H or CH3 Its average molecular weight range is from about 500 to 10,000.
Contain ammonia ester bond (NH-CO-O-) in polyurethane of the present invention (methyl) acrylic ester oligomer. Film and to form the hydrogen bond of acyclic and/or annular between high-polymer molecular by the H atom on the ammonia ester bond and O atom. Masterpiece time spent outside, hydrogen bond is separable and absorb external energy (every mole absorbs 20～25kJ). After removing, external force can again form again hydrogen bond again. So hydrogen bond splits and the more reversible repetition of formation, and making films has high degree of mechanical wearability and toughness; Ammonia ester bond also brings strong tack, good performances such as chemical-resistant, acid and alkali-resistance, high-low temperature resistant and wet-heat resisting for filming in addition.
(methyl) acrylate-functional groups that contains four or more in polyurethane of the present invention (methyl) acrylic ester oligomer, has fast reaction, high crosslink density can be provided, making films has high degree of mechanical wearability and hardness, and has good chemical-resistant etc. When the functional group of polyurethane (methyl) acrylic ester oligomer is less than four, such as polyurethane (methyl) acrylic ester oligomer for two functional groups or trifunctional, because crosslink density is low, abrasion performance is relatively poor, does not reach the requirement of present electronic product and household electrical appliance.
Described polyurethane (methyl) acrylic ester oligomer average molecular weight range is from about 500 to 10,000, and when mean molecule quantity was lower than 500, paint film was firmly crisp, and pliability is very poor; When mean molecule quantity greater than 10,000 o'clock, the resin reaction activity decreased, although the good hardness of the pliability of filming is low, durability, abrasion performance are poor, can not satisfy actual requirement.
Described polyurethane (methyl) acrylic ester oligomer occupies the weight fraction of 20-90 in the present invention usually, is preferably 25-70.
Described reactive diluent is for containing at least (methyl) acrylate monomer of three (methyl) acrylate-functional groups or their mixture, and is concrete such as trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, ethoxyquin trimethylolpropane triacrylate, the third oxidation trimethylolpropane triacrylate, glycerol propoxylate triacrylate, tetramethylol methane tetraacrylate, two contracting trimethylolpropane tetra-acrylate, ethoxyquin tetramethylol methane tetraacrylate, the third oxidation tetramethylol methane tetraacrylate, dipentaerythrityl ether five acrylate, dipentaerythrityl ether six acrylate etc. The characteristics such as it is low that described polyfunctional group (methyl) acrylate monomer has volatility usually, and laser curing velocity is fast, and the cured product crosslink density is large, and hardness is high, and chemical resistance is good, and scratch resistance height and abrasion performance are good. If adopt simple function group or two functional groups (methyl) acrylate monomer as main reactive diluent, then will reduce the crosslink density of whole prescription, abrasion performance there is obvious reduction. In actual applications, viscosity is higher for adopting, and the ink formulations of the polyfunctional monomer that dilution capacity is slightly low can add in addition a small amount of organic solvent and adjust viscosity, so just can not be to the cured product crosslink density, hardness, chemical resistance and abrasion performance etc. is brought negative impact. Described organic solvent can be selected ester class, alcohols, ketone, pure ethers or their mixture.
Described reactive diluent is mainly used to control viscosity in the present invention, the viscosity of its consumption Main Basis prescription and deciding, 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 complete problem of solidification of adding the photocuring system of pigment is a difficult problem always. Because the pigment in the printing ink has strong absorption and reflex to ultraviolet light, light trigger is the initator of bottom particularly, is difficult to absorb sufficient ultraviolet light. Cause curing reaction in order to make initator can decomposite enough active materials, can increase the concentration of initator, but this is effective to surface coating material. Because initator a large amount of absorbing ultraviolet light in top layer arrive the ultraviolet light of bottom still less, the more difficult curing in bottom. Therefore be added with the colored paint of pigment for the bottom is solidified, 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 polyurethane (methyl) acrylate, behind the rete photocuring, because of the reason of oxygen inhibition, it is incomplete surface cure usually to occur, be that bottom solidifies substantially, and the surface is not dry and comfortable, easily produce fingerprint, even the surface become the 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, the see compound of the efficient alpha-alcohol ketone photoinitiator that solidifies of photoinitiator and shallow top layer of the efficient acyl group oxidation that namely is suitable for deeply-curing. More preferably its addition and mixed proportion are controlled, to reach the fully curing that causes top layer and bottom.
The acylphosphine oxide photoinitiator is such as 2; 4; 6-trimethylbenzene formyl diethyl phosphonate, 2; 4; 6-trimethylbenzoyl-ethyoxyl-phenyl phosphine oxide, 2; 4; 6-trimethylbenzene formyl diphenyl phosphine oxide, two (2; 4; the 6-trimethylbenzoyl)-phenyl phosphine oxide, two (2; 6-dimethoxy benzoyl)-(4 ', 4 '-dimethyl octyl group-2) Irgacure 1700, the Irgacure 1800 of phosphine oxide etc. and derived product such as Ciba Specialty Chemicals company, Irgacure 1850, Irgacure 2020, Irgacure 2010, Irgacure 2005, Irgacure 4265 etc.
Irgacure 500, the Irgacure 1000 etc. of alpha-alcohol ketone photoinitiator such as 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylacetone-1,4-(2-hydroxyl ethoxy) phenyl-2-hydroxyl-2-acetone etc. and derived product such as Ciba Specialty Chemicals company.
Acylphosphine oxide photoinitiator and the two mixing of alpha-alcohol ketone 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.
Preferred embodiment of the present invention is the mixture of two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxides and 1-hydroxycyclohexylphenylketone.
Wherein, two (2; 4; the 6-trimethylbenzoyl)-phenyl phosphine oxide can adopt the product I rgacure 819 of Ciba Specialty Chemicals company; it has strong absorption 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 formoxyl and the methyl free radicals of seeing that Norrish I type photolysis produces, and has highly vivaciously, the characteristics of autohemagglutination not, after cracking, namely participates in the initiated polymerization of oligomer and monomer. When the system that contains pigment is subject to when irradiation ultraviolet ray, in layer participates in reaction from table to inner Irgacure 819, 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 discoloration, therefore also are suitable for the White system prescription. Simultaneously, Irgacure 819 good heat stabilities are heated to 180 ℃ without chemical reaction generation, excellent storage stability.
Wherein, the 1-hydroxycyclohexylphenylketone can adopt the product I rgacure 184 of Ciba Specialty Chemicals company. It has not xanthochromia, efficient shallow top layer curing performance, and the characteristics such as low volatility and stable storage are suitable for comprising the initiated polymerization of all colours prescription of varnish.
Two (2; 4; the 6-trimethylbenzoyl)-mixture of phenyl phosphine oxide and 1-hydroxycyclohexylphenylketone in usually the shared part by weight of 1-hydroxycyclohexylphenylketone should be higher than two (2; 4; the 6-trimethylbenzoyl)-phenyl phosphine oxide; the preferred mixed proportion 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 key component, also can contain components more well known in the art in the ink composite of the present invention, such as coloring pigment, filler, pigment dispersing agent, levelling agent, defoamer, adhesion promoter, delustering agent etc., its related content can be referring to US4680368, US4608409 and JP2985536 etc.
Specific embodiment of the present invention is: adopting such as Japan Patent JP2985536B2 when disclosed type siloxane levelling agent realizes that bat printing is crossed outside the glue, also improve bat printing by the interpolation pearl filler and cross the colloidality energy, 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 producing continuously fast on the production line, enhance productivity etc. In addition, can preferably adopt the calcium carbonate through fatty acid treatment, described aliphatic acid such as laurate, stearic acid or other aliphatic acid and composition thereof etc. form multi-level molecular layer coating on the calcium carbonate surface, can obtain good dispersive 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 organic pigment of different this area routines to can be formulated into ink formulations of all kinds, adopt emission spectrum at the common uv lamp of 200-400nm scope, all obtain good curing performance. The present invention's ink formulations of all kinds all has fast continuous bat printing, and it is complete to cross glue, the characteristics of clear patterns; Has fast curing performance, outstanding adhesive force, high abrasion resistance and anti chemical properties etc. Simultaneously; organic solvent content in the ink formulations is low; it is healthy to be conducive to the operator; be conducive to environmental protection; be specially adapted to require abrasion performance and the industries such as chemical resistant electronic product and household electrical appliance, such as mobile phone, computor-keyboard, telephone set, camera, sound equipment, DVD, MP3, electric fan, hair dryer, toaster, wrist-watch etc.
In actual applications, the applicable ground of ink composite of the present invention is very extensive, such as can selecting the plastic cement such as ABS, PC, ABS/PC, PP, TPU, PVC, and all kinds of plastic cement of having primed, metal, alloy etc.
Comparatively preferred scheme of ink composite of the present invention is to contain following component and parts by weight in actual applications:
(1) at least a four or four above functional polyurethane (methyl) acrylic ester oligomer: 20-90 are preferably 25-70;
(2) Photoepolymerizationinitiater initiater: 1-15 is preferably 2-10;
(3) contain at least (methyl) acrylate monomer: 10-85 of trifunctional, be preferably 10-60;
(4) surface tension auxiliary agent: 0.1-2.0 is preferably polyether-modified poly dimethyl silica;
(5) calcium carbonate: 0-50 is preferably 5-30;
(6) dispersant: 0-10
(7) optional colouring agent: 0-80.
According to above-mentioned preferred version, when colouring agent was Chinese white, further preferred ink combination composition formula was: four or four above functional polyurethane (methyl) acrylate: dispersant: titanium dioxide: surface treated calcium carbonate: three or three above functional group (methyl) acrylate monomers: polyether-modified dimethyl silicone polymer: 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 colouring agent is high-carbon black pigment, can be mixed with black ink, its charge ratio is: four or four above functional polyurethane (methyl) acrylate: dispersant: high-carbon black pigment: surface treated calcium carbonate: three or three above functional group (methyl) acrylate monomers: polyether-modified dimethyl silicone polymer: 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 colouring agent is organic red, when organic yellow, organic phthalocyanine etc., can be mixed with red, Huang, indigo plant, the green printing ink that waits. Its charge ratio is: four or four above functional polyurethane (methyl) acrylate: dispersant: colouring agent is (organic red, organic yellow, or organic phthalocyanine): surface treated calcium carbonate: three or three above functional group (methyl) acrylate monomers: polyether-modified dimethyl silicone polymer: Irgacure 819: Irgacure 184=25-90: 1-10: 1-30: 5-30: 10-60: 0.1-2.0: 0.2-5: 1-10.
The specific embodiment
The following examples and reference examples are that the present invention is described further, are not to limit 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 Specialty Chemicals company product
Irgacure 184 1-hydroxycyclohexylphenylketone Ciba Specialty Chemicals company products
HDDA 1, the 6-hexanediyl ester
The TMPTA trimethylolpropane triacrylate
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 dispersant Disperbyk
30.0 parts of titanium dioxides
10.0 parts in surface treated calcium carbonate
16.0 parts of TMPTA
0.2 part of polyether-modified dimethyl silicone polymer
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
Printing ink manufacture technology: with each component in above-described embodiment, mix in described ratio, be ground to fineness＜20 micron, namely obtain corresponding printing ink.
Parameters of construction technology: the ground that is used for evaluation experimental is the polycarbonate plate (thickness 2.0mm) of standard, the ground pre-treatment is cleaned with neutral abluent, adopt small-sized pad printer (trade name: KIPP 100 pad printer, the firm and persistent company in Hong Kong produces), the rectangle metallic plate of wide 15mm, long 35mm, etch depth 20um, shift printing rubber head pressure 6kg/cm2 Ink viscosity is 1200cps, and ink film thickness is 8um.
The ink solidification condition: with workpiece pre-baked 60 ℃/3 minutes first, after the high-pressure mercury-vapor lamp of power output 120W/cm, lamp was apart from about 15em, 3 m/mins of line speeds, exposure time: 4～5 seconds.
Method of testing 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 | Adhesive force | 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 be scrolling RCA wear resistant instrument not after the paper tape of oiling and the sample friction under certain winding number, differentiate the effect of its abrasion. |
| 6 | Alcohol resistance | 1000g diameter 10mm circle copper rod wraps 4 layers of byssus, soaks 99.5% alcohol, back and forth friction, 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, check that film coated surface is whether unusual, gloss has or not significant 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 bicarbonate solution, place 60 ℃, in the 90% humidity climatic chamber, 48 hours, checking films had or not variable color, cracking etc. |
| 10 | Heat-resisting quantity | 80 ℃ of insulating boxs, 240 hours, checking films had or not cracking etc., detects adhesive force. |
| 11 | Lower temperature resistance | -20 ℃ of insulating boxs, 240 hours, checking films had or not cracking etc. |
| 12 | Humidity resistance | 55 ℃, 100% humidity damp heat box, 48 hours, checking films had or not cracking etc., detects adhesive force. |
| 13 | Cold-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, adhesive force, anti-RCA. |
Embodiment 2
50.0 parts of six functional groups aromatic urethane acrylic ester oligomer CN997
163 5.0 parts of dispersant Disperbyk
5.0 parts of high-carbon black pigments
12.0 parts in surface treated calcium carbonate
23.0 parts of TMPTA
0.2 part of polyether-modified dimethyl silicone polymer
819 3.0 parts of Irgacure
184 4.0 parts of Irgacure
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, method of testing and reference standard are with example 1.
Embodiment 3
50.0 parts of six functional groups aromatic urethane acrylic ester oligomer CN997
163 1.5 parts of dispersant Disperbyk
10.0 parts of the organic red pigment of naphthols
10.0 parts in surface treated calcium carbonate
23.0 parts of TMPTA
0.2 part of polyether-modified dimethyl silicone polymer
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, method of testing and reference standard are with embodiment 1.
Embodiment 4
50.0 parts of six functional groups aromatic urethane acrylic ester oligomer CN997
163 2.0 parts of dispersant Disperbyk
12.0 parts of the organic yellow uitramarines of virtue acid amides
10.0 parts in surface treated calcium carbonate
20.0 parts of TMPTA
0.2 part of polyether-modified dimethyl silicone polymer
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, method of testing 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 dispersant Disperbyk
10.0 parts of phthalocyanine blues
10.0 parts in surface treated calcium carbonate
23.0 parts of TMPTA
0.2 part of polyether-modified dimethyl silicone polymer
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, method of testing 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 dispersant Disperbyk
10.0 parts of phthalocyanine greens
10.0 parts in surface treated calcium carbonate
23.0 parts of TMPTA
0.2 part of polyether-modified dimethyl silicone polymer
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, method of testing 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 dispersant Disperbyk
30.0 parts of titanium dioxides
10.0 parts in surface treated calcium carbonate
16.0 parts of TMPTA
0.2 part of polyether-modified dimethyl silicone polymer
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 oligomer at 1: 1, and other components and ratio remain unchanged.
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, method of testing and reference standard are with embodiment 1.
Reference examples 1
264 43.5 parts of trifunctional aliphatic urethane acrylate oligomer Ebecryl
163 1.5 parts of dispersant Disperbyk
30.0 parts of titanium dioxides
10.0 parts in surface treated calcium carbonate
9.5 parts of PETTA
0.2 part of polyether-modified dimethyl silicone polymer
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
This reference examples is on embodiment 1 basis, press the oligomer amount 1: 1, replace the hexafunctional aliphatic urethane acrylates oligomer with trifunctional urethane acrylate Ebecryl 264, substitute TMPTA with PETTA simultaneously and make diluent, and their ratio adjusted, with the impact 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, method of testing and reference standard are with embodiment 1.
Reference examples 2
284 42.0 parts of the two aliphatic urethane acrylate oligomer Ebecryl of functional group
163 1.5 parts of dispersant Disperbyk
30.0 parts of titanium dioxides
11.0 parts in surface treated calcium carbonate
16.0 parts of PETTA
0.2 part of polyether-modified dimethyl silicone polymer
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
This reference examples is on embodiment 1 basis, press the oligomer amount 1: 1, replace the hexafunctional aliphatic urethane acrylates oligomer with trifunctional urethane acrylate Ebecryl 284, substitute TMPTA with PETTA simultaneously and make diluent, and their ratio adjusted, with the impact 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, method of testing 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 dispersant Disperbyk
30.0 parts of titanium dioxides
10.0 parts in surface treated calcium carbonate
16.0 parts of TMPTA
0.2 part of polyether-modified dimethyl silicone polymer
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 oligomer at 1: 1, and other components and ratio remain unchanged.
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, method of testing 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 dispersant Disperbyk
30.0 parts of titanium dioxides
10.0 parts in surface treated calcium carbonate
16.0 parts of TMPTA
0.2 part of polyether-modified dimethyl silicone polymer
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 oligomer at 1: 1, and other components and ratio remain unchanged.
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, method of testing 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 dispersant Disperbyk
30.0 parts of titanium dioxides
10.0 parts in surface treated calcium carbonate
16.0 parts of HDDA
0.2 part of polyether-modified dimethyl silicone polymer
819 2.0 parts of Irgacure
184 4.0 parts of Irgacure
This reference examples is on embodiment 1 basis, only uses HDDA to replace TMPTA at 1: 1, and other components and ratio remain unchanged.
Printing ink manufacture technology, parameters of construction technology, ink solidification condition, method of testing 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 | Without wire drawing, without horizontal infiltration; It is complete to cross glue, clear patterns. | Without wire drawing, without horizontal infiltration; It is complete to cross glue, clear patterns. | Without wire drawing, without horizontal infiltration; It is complete to cross glue, clear patterns. | Without wire drawing, without horizontal infiltration; It is complete to cross glue, clear patterns. | Without wire drawing, without horizontal infiltration; It is complete to cross glue, clear patterns. | Without wire drawing, without horizontal infiltration; It is complete to cross glue, clear patterns. |
| 3 | Adhesive force | 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 | Heat-resisting quantity | 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-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 | Without wire drawing, without 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 not. | Slight wire drawing and horizontal infiltration are arranged; It is complete to cross glue, but pattern is clear not. | Slight wire drawing and horizontal infiltration are arranged; It is complete to cross glue, but pattern is clear not. | Slight wire drawing and horizontal infiltration are arranged; It is complete to cross glue, but pattern is clear not. | It is imperfect to cross glue. |
| 3 | Adhesive force | 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 | Heat-resisting quantity | By | / | / | / | / | / |
| 11 | Lower temperature resistance | By | / | / | / | / | / |
| 12 | Humidity resistance | By | / | / | / | / | / |
| 13 | Cold-hot alternation performance | By | / | / | / | / | / |
Annotate: "/" represents that this Xiang Wei tests
Estimate: by relatively can finding out of embodiment and reference examples; 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 diluent; inorganic and/or organic pigment is made colouring agent; and the compound of acylphosphine oxide and α monohydroxy 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 simultaneously fast curing performance; outstanding adhesive force; high rigidity; acid and alkali-resistance; high-low temperature resistant; wet-heat resisting, the characteristics such as chemical proof and environmental protection can satisfy the requirement of present electronic product and household electrical appliance. And that the propenoic methyl carbamate oligomer of two functional groups of low degree of functionality and trifunctional is done the base-material abrasion resistance is lower, 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, can find out from the result of reference examples still not reach higher abrasion resistance. Simultaneously, the acrylate monomer of simple function group and two functional groups is as main reactive diluent, and the abrasion performance of prescription and bat printing are crossed colloidality can obvious impact. 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 producing continuously fast on the production line, has improved production efficiency etc.
Claims (13)
- 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 polyurethane (methyl) acrylic ester oligomer: 20-90;(2) Photoepolymerizationinitiater initiater: 1-15;(3) reactive diluent: 10-85;Described polyurethane (methyl) acrylic ester oligomer contains four (methyl) acrylate-functional groups at least, and described reactive diluent is the acrylate that contains three or three above hydroxy functional groups.
- 2, ultraviolet cured printing ink composition according to claim 1, it is characterized in that described polyurethane (methyl) acrylic ester oligomer can obtain isocyanate terminated prepolymer by prepolymer and the isocyanate reaction of terminal hydroxy group, (methyl) acrylate reactions of prepolymer and hydroxy-functional obtains thus again.
- 3, ultraviolet cured printing ink composition according to claim 1 is characterized in that described Photoepolymerizationinitiater initiater adopts the mixture of acylphosphine oxide photoinitiator and alpha-alcohol ketone photoinitiator.
- 4, ultraviolet cured printing ink composition according to claim 1 is characterized in that described reactive diluent is selected from trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, ethoxyquin trimethylolpropane triacrylate, the third oxidation trimethylolpropane triacrylate, glycerol propoxylate triacrylate, tetramethylol methane tetraacrylate, two contracting trimethylolpropane tetra-acrylate, ethoxyquin tetramethylol methane tetraacrylate, the third oxidation tetramethylol methane tetraacrylate, dipentaerythrityl ether five acrylate, dipentaerythrityl ether six acrylate or their mixture.
- 5, ultraviolet cured printing ink composition according to claim 1 is characterized in that the mean molecule quantity of described polyurethane (methyl) acrylic ester oligomer is 500-10,000.
- 6, ultraviolet cured printing ink composition according to claim 1 is characterized in that also comprising one or more in coloring pigment, filler, pigment dispersing agent, levelling agent, defoamer, adhesion promoter and the delustering agent.
- 7, ultraviolet cured printing ink composition according to claim 1 is characterized in that also comprising pearl filler, levelling agent, coloring pigment and pigment dispersing agent.
- 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 oligomer: 20-90;(2) Photoepolymerizationinitiater initiater: 1-15;(3) contain at least (methyl) acrylate monomer: 10-85 of trifunctional;(4) surface tension auxiliary agent: 0.1-2.0;(5) calcium carbonate: 0-50;(6) dispersant: 0-10;(7) optional colouring agent: 0-80.
- 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: dispersant: titanium dioxide: surface treated calcium carbonate: three or three above functional group (methyl) acrylate monomers: polyether-modified dimethyl silicone polymer: Irgacure 819: Irgacure 184=20-90: 0-5.0: 1-60: 5-50: 10-85: 0.1-2.0: 0.1-3: 1-8.
- 10, ultraviolet cured printing ink composition claimed in claim 8 when it is characterized in that described colouring agent is high-carbon black pigment, can be mixed with black ink.
- 11, ink composite claimed in claim 10 is characterized in that the charge ratio of black ink is: four or four above functional polyurethane (methyl) acrylate: dispersant: high-carbon black pigment: surface treated calcium carbonate: three or three above functional group (methyl) acrylate monomers: polyether-modified dimethyl silicone polymer: Irgacure 819: Irgacure 184=20-90: 1-10: 0.1-15: 5-50: 10-85: 0.1-2.0: 0.2-5: 1-10.
- 12, ink composite claimed in claim 8 is characterized in that described colouring agent is organic red, organic yellow, when organic phthalein is blue or green, can be mixed with red, Huang, indigo plant, green ink.
- 13, the described ink composite of claim 12, four or four above functional polyurethane (methyl) acrylate: dispersant: colouring agent is (organic red, organic yellow, or organic phthalocyanine): surface treated calcium carbonate: three or three above functional group (methyl) acrylate monomers: polyether-modified dimethyl silicone polymer: Irgacure 819: Irgacure 184=20-90: 1-10: 1-80: 5-50: 10-85: 0.1-2.0: 0.2-5: 1-10.
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