CN101993629A - Transfer printing type ultraviolet light curing ink composition, preparation method thereof and mobile phone casing using ink composition - Google Patents
Transfer printing type ultraviolet light curing ink composition, preparation method thereof and mobile phone casing using ink composition Download PDFInfo
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- CN101993629A CN101993629A CN200910109440XA CN200910109440A CN101993629A CN 101993629 A CN101993629 A CN 101993629A CN 200910109440X A CN200910109440X A CN 200910109440XA CN 200910109440 A CN200910109440 A CN 200910109440A CN 101993629 A CN101993629 A CN 101993629A
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Abstract
The invention provides a transfer printing type ultraviolet light curing ink composition and a preparation method thereof. The ink composition comprises main body resin, a thinner, pigment and photoinitiators, and addition agents are included or not included, wherein the main body resin is polyester acrylate resin, modified acrylic resin, high-functionality-degree aliphatic urethane acrylate and hydroxy acrylic resin, the hydroxy acrylic resin is thermoplastic hydroxy acrylic resin, and the hydroxyl value content is between 45 and 70 mg KOH/g. The invention also provides a mobile phone casing using the ink composition, wherein the mobile phone casing sequentially comprises a substrate, a primer layer, a gloss oil layer and an ink pattern layer from bottom to top, and the ink pattern layer is obtained from the ink composition through transfer printing. When the transfer printing type ultraviolet light curing ink composition is adopted, the adhesive force between the ink layer and a contact layer can be enhanced, and in addition, when the surface of the contact layer is lower, the cured ink layer can effectively avoid the phenomenon of edge contraction.
Description
Technical field
But the present invention relates to a kind of UV curable ink composition and method of making the same of bat printing and the handset shell that uses this ink composite.
Background technology
But the UV-light of bat printing (UV) curing inks is the focus of Recent study, and the UV pad-transfer printing ink has high glossiness and high-wearing feature and excellent environment resistivity all makes solvent borne printing ink prove definitely inferior.
Pad-transfer printing ink needs high opacifying power usually, and this depth of shade and fineness requirement to pigment is very high, but because the birth defect of bat printing process transfer effect, high solid component content will influence the performance of opacifying power, and this is that pad-transfer printing ink is made difficult reason.The unification of in fact more difficult acquisition high covering power of UV pad-transfer printing ink and high curing rate.High curing rate means high transparent and relative thin China ink layer, but this is that high covering power institute is unallowed.At present, commercially available UV pad-transfer printing ink (is that meticulous mesh is transferred printing in order to obtain meticulous printing effect, can reach 140～150 line/inches or higher), and the unification of high covering power, high curing rate and high adhesive force, the UV pad-transfer printing ink has been taked the multiple inks compounding technique, for example, the UV pad-transfer printing ink of MARABU company has been taked the multiple inks compounding technique, it more similarly is the technology that adds multiple manufacturing printing ink in the system of UV printing ink, as two-pack or solvent type ink, just obtained the relative equilibrium of these character.But when on this ink composite interface lower attached to surface energies such as gloss oil, still exist sticking power relatively poor, solidify the rear section product and the phenomenon that the edge shrinks occurs.
And common high temperature sintering type, low temperature curing type printing ink can occur dot gain or lines inevitably and broaden in drying process, can't carry out meticulous printing.
But disclose a kind of UV curable ink composition of bat printing in the prior art, 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, and described reactive thinner is the acrylate that contains three or three above hydroxy functional groups.This ink composite attached on the lower interface of surface energies such as gloss oil the time, still exist sticking power relatively poor, solidify the rear section product and the phenomenon that the edge shrinks occurs, cause dim pattern unclear, the yield of product descends.
Summary of the invention
The technical problem to be solved in the present invention is on the lower interface of surface energy the time, and sticking power is relatively poor, solidify the rear section product problem that the edge shrinks occurs.
But the invention provides a kind of UV curable ink composition of bat printing, described composition contains matrix resin, thinner, pigment and light trigger, contain or do not contain auxiliary agent, wherein, described matrix resin is polyester acrylic resin, acrylic resin modified, high functionality aliphatic urethane acrylate and Hydroxylated acrylic resin, described Hydroxylated acrylic resin is thermoplastics type's Hydroxylated acrylic resin, and hydroxyl value content is at 45-70mgKOH/g.
But a kind of UV curable ink preparation of compositions method of above-mentioned bat printing, this method comprises that matrix resin, thinner, pigment mix, grinding obtains, described ink composite contains matrix resin, thinner, pigment and light trigger, contain or do not contain auxiliary agent, wherein, described matrix resin is polyester acrylic resin, acrylic resin modified, high functionality aliphatic urethane acrylate and Hydroxylated acrylic resin, described Hydroxylated acrylic resin is thermoplastics type's Hydroxylated acrylic resin, and hydroxyl value content is at 45-70mgKOH/g.
A kind of handset shell, this handset shell comprises base material, prime coat, gloss oil layer, ink design layer successively from the end to the face, described ink design layer is that above-mentioned ink composite obtains through bat printing, described composition contains matrix resin, thinner, pigment and light trigger, contain or do not contain auxiliary agent, wherein, described matrix resin is polyester acrylic resin, acrylic resin modified, high functionality aliphatic urethane acrylate and Hydroxylated acrylic resin, described Hydroxylated acrylic resin is thermoplastics type's Hydroxylated acrylic resin, and hydroxyl value content is at 45-70mgKOH/g.
But adopt the UV curable ink composition of above-mentioned bat printing, adopt this pad-transfer printing ink composition, can improve the sticking power between ink lay and the contact layer, and when the surface energy of this contact layer is low, the phenomenon that makes the ink lay after the curing avoid the edge to shrink effectively.Use the clear patterns of ink design layer of the handset shell of this ink composite, the yield of product is effectively improved.
Embodiment
But a kind of UV curable ink composition of bat printing, described composition contains matrix resin, thinner, pigment and light trigger, contain or do not contain auxiliary agent, wherein, described matrix resin is polyester acrylic resin, acrylic resin modified, high functionality aliphatic urethane acrylate and Hydroxylated acrylic resin, described Hydroxylated acrylic resin is thermoplastics type's Hydroxylated acrylic resin, and hydroxyl value content is at 45-70mgKOH/g.
The present inventor finds through a large amount of experiments, when described matrix resin is polyester acrylic resin, acrylic resin modified, high functionality aliphatic urethane acrylate and Hydroxylated acrylic resin, and Hydroxylated acrylic resin is thermoplastics type's Hydroxylated acrylic resin, hydroxyl value content is when 45-70mgKOH/g, the sticking power of this ink composite is greatly improved than the sticking power of prior art, and the shrinking percentage of ink lay reduces greatly simultaneously.
Add the thermoplastic acrylic resin of high hydroxyl value (hydroxyl value content is 45-70mgKOH/g) in the UV pad-transfer printing ink prescription of the present invention, the temperature under the UV light irradiation can form the crosslinked of densification, and can not react under the room temperature.Described Hydroxylated acrylic resin hydroxyl value content is between 45-70mgKOH/g, but at 50-60 ℃ of following fast setting, therefore by UV light irradiation ink composite of the present invention the time, lamp can make this Hydroxylated acrylic resin completely solidified according to temperature.Because existing single UV resin is solvent-free, self is dry slow, behind the gloss oil surface printing of utmost point low surface energy, interfacial effect produces the cissing phenomenon, the present invention adds thermoplastics type's Hydroxylated acrylic resin in the UV resin, this Hydroxylated acrylic resin has quick-drying character, solves the problem that the ink lay edge shrinks when solidifying.Simultaneously, because the edge no longer shrinks, the sticking power of ink lay of the present invention and contact layer has also obtained further raising.
The present invention adopts the matrix resin of the mixture of high functionality resin and low functionality resin as UV curable ink simultaneously, wherein, the high functionality resin is that functionality is the aliphatic urethane acrylate of 6-9, and low functionality resin is that functionality is the acrylic resin modified of 2-4 or polyester acrylic resin.The functional group of high functionality resin is more, the reactive behavior height, and the crosslinking curing degree is also high, and it is crosslinked to be easy to form build in solidification process, and has bigger cure shrinkage (cure shrinkage can reach more than 10% sometimes).Thereby the paint film that forms behind ultraviolet light polymerization has very high wear resistance and hardness, but low relatively functionality resin, its sticking power is a bit weaker.And the general viscosity of pure high functional group resin is bigger, so workability is bad.Low functionality ester resin is because the double key number order is few, so its reactive behavior is relatively low, and the crosslinking curing degree is low, and cure shrinkage is also less.Thereby the paint film that forms behind ultraviolet light polymerization has higher snappiness, and ground is had higher sticking power.Based on above-mentioned low functionality resin and high functionality resin relative merits separately, take all factors into consideration the wear resistance of paint film, hardness, snappiness, sticking power and workability etc. can be used the two, make the coating of formation reach the excellent comprehensive performance.And, can reasonably regulate kind and the ratio of the two according to difference to the various performance requriementss of printing ink.
Gross weight with ink composite is a benchmark, the content of described matrix resin is 55-80 weight %, and the content of described thinner is 10-15 weight %, and the content of described pigment is 5-25 weight %, the content of described light trigger is 4-6 weight %, and the content of described auxiliary agent is 0-10 weight %.
Gross weight with ink composite is a benchmark, the content of described polyester acrylic resin is 30-40 weight %, acrylic resin modified content is 15-20 weight %, the content of high functionality aliphatic urethane acrylate is 5-10 weight %, and the content of Hydroxylated acrylic resin is 5-10 weight %.
Described polyester acrylic resin role is improved the cured film mechanical mechanics property for improving solidification rate, and simultaneously as millbase, dispersing of pigments is good.
Described acrylic resin modified for amination acrylic resin or propylene dichloride acid resin, acrylic resin modifiedly can impel that printing ink of the present invention is further fast to be done.
Acrylic resin modified functionality is 2, and the functionality of described high functionality aliphatic urethane acrylate is 6-9, and the functionality of described polyester acrylic resin is 2-4.
Described thinner is a UV-curable monomer, and described UV-curable monomer is the single functionality monomer, and the monomeric surface energy of this single functionality is 22-30Dyne/cm.Played the effect that reduces the surface energy of ink composite, the surface energy of ink composite is than the low ability of the surface energy drawout of base material.
Preferably, described ink composite also contains second UV-curable monomer, described second UV-curable monomer is the three-functionality-degree monomer, and this three-functionality-degree monomer has low character of shrinking, and makes the shrinking percentage of ink composite further reduce the shrinking percentage of ink composite.Preferably, be benchmark with the gross weight of ink composite, the content of described second UV-curable monomer is 5-10 weight %.
But the UV curable ink preparation of compositions method of above-mentioned bat printing, this method comprises that matrix resin, thinner, pigment mix, grinding obtains, described ink composite contains matrix resin, thinner, pigment and light trigger, contain or do not contain auxiliary agent, wherein, described matrix resin is polyester acrylic resin, acrylic resin modified, high functionality aliphatic urethane acrylate and Hydroxylated acrylic resin, described Hydroxylated acrylic resin is thermoplastics type's Hydroxylated acrylic resin, and hydroxyl value content is at 45-70mgKOH/g.
A kind of handset shell, this handset shell comprises base material, prime coat, gloss oil layer, ink design layer successively from the end to the face, described ink design layer is that above-mentioned ink composite obtains through bat printing, described ink composite contains matrix resin, thinner, pigment and light trigger, contain or do not contain auxiliary agent, wherein, described matrix resin is polyester acrylic resin, acrylic resin modified, high functionality aliphatic urethane acrylate and Hydroxylated acrylic resin, described Hydroxylated acrylic resin is thermoplastics type's Hydroxylated acrylic resin, and hydroxyl value content is at 45-70mgKOH/g.
Wherein, undercoat is in order to make workpiece have background color, and the gloss oil layer is the priming paint that is used for protecting on the workpiece, and ink design layer is in order to make workpiece can have required pattern.
Described gloss oil can be the UV bat printing gloss oil of various routines.Can be commercially available, for example five hide the full light UV780 of UV.
The surface energy of described gloss oil layer is 22-30Dyne/cm.
Light trigger kind described in the printing ink of the present invention and consumption are conventionally known to one of skill in the art, described light trigger is two or more composite light trigger, pigment according to printing ink comes the selective light initiator, and it is the common practise of this area that the difference of the wavelength that absorbs according to different pigment is selected different light triggers.For example, described light trigger can be selected from IHT-PI185, IHT-PI907, Irgacure651, Irgacure184, Irgacure369, Irgacure754, Irgacure2022, darocur1173, one or more among the darocurMBF.Wherein IHT-PI series is Chinese domestic goods, Irgacure, and darocur series is Switzerland vapour Bagong department product, its trade mark is conventionally known to one of skill in the art.With the total weight is benchmark, and the content of described light trigger is that the content of light trigger is 4-6 weight %.
Described auxiliary agent refers to one or more in UV curable ink flow agent commonly used, defoamer, thixotropic agent, the dispersion agent.The kind of these auxiliary agents and consumption are conventionally known to one of skill in the art.
Flow agent described in the present invention mainly is in order to guarantee the surface effect of coating excellence, the kind of flow agent and consumption are conventionally known to one of skill in the art, for example described flow agent can be selected from EFKA3883, EFKA3886, EFKA3600, BYK366, BYK333, among BYK307, the DEGO410 one or more.Wherein EFKA series is Dutch Ai Fuka company product, and BYK series is BYK company product, and DEGO series is German Di Gao company product, more than its trade mark be conventionally known to one of skill in the art.With the total weight is benchmark, and the content of described flow agent is 0-2 weight %, is preferably 0-1.5 weight %.
The kind of the defoamer described in the printing ink of the present invention and consumption are conventionally known to one of skill in the art, and for example, described defoamer can be selected from EFKA2022, EFKA2527, EFKA2040, BYK352, BYK354, among the BYK357 one or more.With the total weight is benchmark, and the content of described defoamer is 0-2 weight %, is preferably 0-1.5 weight %.
Dispersion agent described in the printing ink of the present invention refers to any material that can improve described matrix resin dispersion state in solvent, as Kerper-602, and Kerper-605, Kerper630, CFC-500HP, CFC-510, CFC-637, one or more among the CFC-604S.Wherein Kerper series is U.S. Kerper company product, and CFC series is French CFC company product.With the total weight is benchmark, and the content of described dispersion agent is that 0-5 weight % is preferably 0-3 weight %.
Described thixotropic agent can be the various thixotropic agent that are used for printing ink of routine, for example described thixotropic agent can be in nano-calcium carbonate, nano-calcium carbonate magnesium, nano barium carbonate, nano barium sulfate, nanometer calcium sulfate, aerosil and the organobentonite one or more, the size of described thixotropic agent has no particular limits, under the preferable case, the average particle diameter of described thixotropic agent is a rice in the 10-90.The content of described thixotropic agent is 0-3 weight %.
Described pigment can be the pigment of various routines, be in carbon black, titanium dioxide, pearlescence, pearl powder, aluminium paste, silver-colored slurry, azo pigment and the blue or green pigment of phthalein one or more, can select according to the difference of printed patterns, for example, described pigment can be commercially available, for example Clariant company produce 1533,1541,7005s and 1441.
Below by embodiment the present invention is described in more detail.
Embodiment 1
But the UV curable ink composite formula of the present invention's bat printing is:
Four functionality polyester acrylic resin 38.5wt%
Amino modified acrylic resin 15wt%
Nine functionality aliphatic urethane acrylate 10wt%
Hydroxyl value content is the thermoplastic Hydroxylated acrylic resin 8wt% of 45mgKOH/g
Thinner UV-curable monomer 10wt%
Light trigger 4wt%
Pigment is carbon black 10wt%
Defoamer 0.5wt%
Flow agent 1.5wt%
Thixotropic agent is aerosil 2.0wt%
Dispersion agent 0.5wt%
According to prescription that each component thorough mixing is even, using three-roll grinder to grind until fineness is below the 10 μ m, but obtains the UV curable ink composition A1 of bat printing of the present invention.
Is the gloss oil laminar surface of 28Dyne/cm by the pad printer bat printing in surface energy, and transmits ultra violet lamp by two 60W/cm by conveying belt, and the time is 3min, and the printing ink completely solidified obtains thickness and be 500 in the ink lay A11 sample of 18 μ m.
Embodiment 2
Be also to contain second UV-curable monomer with the difference of embodiment 1, described second UV-curable monomer is the three-functionality-degree monomer.Wherein, the content of four functionality polyester acrylic resins is 30.5wt%, and the monomeric content of three-functionality-degree is 8wt%.But obtain the UV curable ink composition B1 of bat printing of the present invention.
By pad printer bat printing, curing, obtain 500 in ink lay B11 sample.
Embodiment 3
Be not contain auxiliary agent with the difference of embodiment 1, wherein, the content of auxiliary agent flow agent, defoamer, thixotropic agent, dispersion agent is 0, and the content of propylene dichloride acid resin is 19.5wt%.Because of the time of not containing auxiliary agent so mix will be grown than embodiment 1.But obtain the UV curable ink composition C1 of bat printing of the present invention.
By pad printer bat printing, curing, obtain 500 in ink lay C11 sample.
Embodiment 4
Be that with the difference of embodiment 1 nine functionality aliphatic urethane acrylates are changed to six functionality aliphatic urethane acrylates.But obtain the UV curable ink composition D1 of bat printing of the present invention.
By pad printer bat printing, curing, obtain 500 in ink lay D11 sample.
Embodiment 5
Be that with the difference of embodiment 1 four functionality polyester acrylic resins are changed to two functionality polyester acrylic resins.But obtain the UV curable ink composition E1 of bat printing of the present invention.
By pad printer bat printing, curing, obtain 500 in ink lay E11 sample.
Embodiment 6
Be that with the difference of embodiment 1 the hydroxyl value content of Hydroxylated acrylic resin is 70mgKOH/g.
But obtain the UV curable ink composition F 1 of bat printing of the present invention.
By pad printer bat printing, curing, obtain 500 in ink lay F11 sample.
Comparative Examples 1
Be not contain four functionality polyester acrylic resins with the difference of embodiment 1, the content of nine functionality aliphatic urethane acrylates is 48.5wt%.But obtain the UV curable ink composition X1 of bat printing.
By pad printer bat printing, curing, obtain 500 in ink lay X11 sample.
Comparative Examples 2
Be that with the difference of embodiment 1 the hydroxyl value content of Hydroxylated acrylic resin is 35mgKOH/g.But obtain the UV curable ink composition Y1 of bat printing.
By pad printer bat printing, curing, obtain 500 in ink lay Y11 sample.
Performance test
The ink lay outward appearance is observed: the printing effect of visual inspection outward appearance ink lay outward appearance, compare with standard model plate pattern, and whether whether the pattern of the ink design layer of bat printing is clear with respect to model, have the edge to shrink or the pit phenomenon.Clear and non-flanged is shunk or the pit phenomenon is OK.Dim design, edge shrink or pit is NG.Wherein, the ratio of the number of OK sample and total number of samples amount (promptly 500) is the yield of product.
Wear resistance is measured: the 7-IBB type RCA abrasion instrument that uses U.S. Nuo Man Instrument and Equipment Company to produce, and under the effect of 175 gram forces, the ink lay after the mill printing, after rubber wheel rotates 500 times, whether the observation ink lay exposes lower floor's ground of ink lay, does not expose to be OK, exposes to be NG.
Sticking power is measured: draw 100 1 millimeter * 1 millimeter square lattice at sprayed surface with drawing the lattice device, the model of producing with Minnesota Mining and Manufacturing Company is 600 smooth being bonded on the grid of scotch tape, do not stay a space, vertically uncover with utmost dispatch then, observe cut edge and have or not depainting.Is 5B as the depainting amount between 0-5%, is 4B between 5-10%, is 3B between 10-20%, is 2B between 20-30%, is B between 30-50%, is being 0B more than 50%.
Alcohol resistance test: dip in full raw spirit (concentration 〉=99.5%) with textile cloth, wrap on the 500g counterweight head of special use and (to wrap that the area of measuring head is about 1cm behind the cotton
2), with 40 times/minute～60 times/minute speed, the stroke about 20mm, 500 circulations of wiping back and forth on the ink lay surface.Not exposing ground is OK, exposes to be NG.
As shown in table 1 by the material property that above-mentioned condition makes
Table 1
From the test result of last table 1 as can be seen, when the ink design layer that is printed on the gloss oil laminar surface that embodiment of the invention 1-6 prepares increases than the sticking power of Comparative Examples 1-2, effectively improved the yield of product, use the clear patterns of ink design layer of the handset shell of this ink composite, the problem that makes most of product avoid the ink lay edge to shrink.
Claims (13)
1. but the UV curable ink composition of a bat printing, described ink composite contains matrix resin, thinner, pigment and light trigger, contain or do not contain auxiliary agent, wherein, described matrix resin is polyester acrylic resin, acrylic resin modified, high functionality aliphatic urethane acrylate and Hydroxylated acrylic resin, described Hydroxylated acrylic resin is thermoplastics type's Hydroxylated acrylic resin, and hydroxyl value content is at 45-70mgKOH/g.
2. but the UV curable ink composition of bat printing according to claim 1, gross weight with ink composite is a benchmark, the content of described matrix resin is 55-80 weight %, the content of described thinner is 10-15 weight %, the content of described pigment is 5-25 weight %, the content of described light trigger is 4-6 weight %, and the content of described auxiliary agent is 0-10 weight %.
3. but the UV curable ink composition of bat printing according to claim 2, gross weight with ink composite is a benchmark, the content of described polyester acrylic resin is 30-40 weight %, acrylic resin modified content is 15-20 weight %, the content of high functionality aliphatic urethane acrylate is 5-10 weight %, and the content of Hydroxylated acrylic resin is 5-10 weight %.
But 4. the UV curable ink composition of bat printing according to claim 1, described acrylic resin modified be amination acrylic resin or propylene dichloride acid resin.
But 5. the UV curable ink composition of bat printing according to claim 1, acrylic resin modified functionality is 2, and the functionality of described high functionality aliphatic urethane acrylate is 6-9, and the functionality of described polyester acrylic resin is 2-4.
But 6. the UV curable ink composition of bat printing according to claim 1, described thinner is a UV-curable monomer, and described UV-curable monomer is the single functionality monomer, and the monomeric surface energy of this single functionality is 22-30Dyne/cm.
7. but the UV curable ink composition of bat printing according to claim 1, described auxiliary agent is one or more in flow agent, defoamer, thixotropic agent, the dispersion agent.
8. but one or more in the UV curable ink composition of bat printing according to claim 1, the described pigment blue or green pigment that is carbon black, titanium dioxide, pearlescence, pearl powder, aluminium paste, silver-colored slurry, azo pigment and phthalein.
9. but according to the UV curable ink composition of any described bat printing of claim 1-8, described ink composite also contains second UV-curable monomer, and described second UV-curable monomer is the three-functionality-degree monomer.
10. but the UV curable ink composition of bat printing according to claim 9 is a benchmark with the gross weight of ink composite, and the content of described second UV-curable monomer is 5-10 weight %.
11. but the UV curable ink preparation of compositions method of the described bat printing of claim 1, it is characterized in that, this method comprises matrix resin, thinner, pigment mixes, grinding obtains, described ink composite contains matrix resin, thinner, pigment and light trigger, contain or do not contain auxiliary agent, wherein, described matrix resin is the polyester acrylic resin, acrylic resin modified, high functionality aliphatic urethane acrylate and Hydroxylated acrylic resin, described Hydroxylated acrylic resin is thermoplastics type's Hydroxylated acrylic resin, and hydroxyl value content is at 45-70mgKOH/g.
12. handset shell, this handset shell comprises base material successively from the end to the face, prime coat, the gloss oil layer, ink design layer, described ink design layer is that any described ink composite obtains through bat printing among the claim 1-8, described composition contains matrix resin, thinner, pigment and light trigger, contain or do not contain auxiliary agent, wherein, described matrix resin is the polyester acrylic resin, acrylic resin modified, high functionality aliphatic urethane acrylate and Hydroxylated acrylic resin, described Hydroxylated acrylic resin is thermoplastics type's Hydroxylated acrylic resin, and hydroxyl value content is at 45-70mgKOH/g.
13. handset shell according to claim 12 is characterized in that, the surface energy of described gloss oil layer is 22-30Dyne/cm.
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Application publication date: 20110330 |