CN1156160A - Ink - Google Patents
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- CN1156160A CN1156160A CN 96111639 CN96111639A CN1156160A CN 1156160 A CN1156160 A CN 1156160A CN 96111639 CN96111639 CN 96111639 CN 96111639 A CN96111639 A CN 96111639A CN 1156160 A CN1156160 A CN 1156160A
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- printing ink
- printing
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- ink
- compound
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Abstract
A printing ink for radiation curing, e.g. by UV radiation or an electron beam comprises a mixture of a polymerisable composition, a pigment or a dye and a titanium or zirconium compound which is an alkoxide of an unsaturated alcohol, said polymerisable composition comprising at least one unsaturated monomer and, optionally, at least one prepolymer and being polymerisable by exposure to radiation. The titanium or zirconium compound acts as an adhesion promoter for the ink.
Description
The present invention relates to printing ink, particularly relate to and containing as the titanium compound of adhesion promotor or the printing ink of zirconium thing.
As everyone knows, the compound as adhesion promotor can prepare with the sequestrant that resembles methyl ethyl diketone and so on from four titan-alkoxides or four molten oxygen base zirconiums.This compound is the compound that can buy and use always, and it is two (acetylacetonate) diisopropoxy titanium, and commodity are called TILCOM TAA, can buy from Tioxide Specialties Limited.
A kind of special purpose of this compound is as a kind of short stick in printing ink.Printing ink is basically by polymer binder, and solvent (normally organic solvent) and pigment and/or dyestuff are formed.Described adhesion promotor is required to promote that printing ink adheres on the substrate that is printed.Usually, it is crosslinked that short stick also makes polymer binder.When joining the printing ink that is used for packing business when particularly joining on the printing ink of the substrate that is used to be printed onto difficulty such as the nitrocellulose on the compound oriented polypropylene, this adhesion promotor is useful especially.
The drying of this printing ink comprises the removal of solvent.But, the pressure limitation of environment aspect solution is dispersed in the atmosphere, exist simultaneously the concern of long-term exposure in the toxic effect of solvent.Therefore, use the solventless ink through the formation of vinyl addition polymerization of radiation-hardenable more and more.Except pigment and/or dyestuff, this printing ink contains functional vinyl monomer and (solidifying rather than electrocuring for UV) one or more light triggers.In general, be used for the ethylene unit of UV solidified printing ink based on acrylate or methacrylic ester.
The printing ink of radiation curing of the present invention comprises that polymerisable composition, pigment or dyestuff and itself are a kind of titanium of alcoxylates of unsaturated alcohol or the mixture of zirconium compounds, described polymerisable composition comprises at least a unsaturated monomer and optional at least a prepolymer, can be by being exposed to polymerization under the radiation.
Now find unexpectedly as according to the titanium compound of a component of printing ink of the present invention or printing ink that zirconium compounds has improved radiation curing binding property difficult adherent substrate such as compound oriented polypropylene.
The unsaturated alcohol of deriving titanium compound or zirconium compounds preferably contains the alkenols of maximum 8 carbon atoms, more preferably contains the alkenols of maximum 6 carbon atoms.Representational alcohol comprises vinyl carbinol, butenol, pentenol and cyclohexenol and chain hexenol.Preferred alcohol is pentenol, such as 2-methyl-3-butene-2-pure and mild 3-methyl-2-butene-1-alcohol.
Be used for the alkoxy compound that titanium compound of the present invention or zirconium compounds are unsaturated alcohols.As a result, described compound contains the group of at least one tool R-O-X general formula, and wherein R preferably contains at the most the alkenyl of 8 carbon atoms or the alkenyl of replacement, and X represents titanium or zirconium.In the practicality, described compound has general formula (RO)
4X, R is identical with the above-mentioned definition of X in the formula.
Yet described titanium compound or zirconium compounds also can contain numerous other groups.For example, can prepare used compound from titan-alkoxide such as the tetraisopropoxy titanium that can buy easily.Be suitable for that compound among the present invention can produce alkoxyl group by only be substituted in some alkoxyl groups (as isopropoxy) this compound by a group of deriving from unsaturated alcohol, the alkenyloxy compound prepares.When using alkoxyl group, alkenyloxy compound, preferred alkoxyl group is methoxyl group, oxyethyl group, propoxy-, butoxy, hexyloxy or octyloxy.
The shortcoming that use contains from the titanium compound of the group of more rudimentary saturated alcohol or zirconium compounds is may discharge parent alcohol when the curing of printing ink of the present invention.As noted earlier, this is unacceptable aspect environment.Thereby the preferred form of titanium compound or zirconium compounds is based on chelating ligand such as alkanolamine, beta-diketon or ethylene glycol.The ligand that is fit to comprises trolamine, tri-isopropanolamine, ethyl ketone acetone, methyl aceto acetate, ethylene glycol and propylene glycol.The other preferred form of titanium compound or zirconium compounds is the compound that comes from the tool higher-boiling compound.Therefore, the derivative of Diethylene Glycol or propylene glycol can successfully be used as the component of printing ink of the present invention.
If described compound is discharged by titanium compound or zirconium compounds, so another embodiment utilized can be in polymerisable composition as titanium derivative or the zirconium derivative of monomeric compound.For example, the titanium of acrylic or methacrylic acid or zirconium derivative are particularly suitable for acting on titanium compound of the present invention or zirconium compounds.Although preferred unsaturated acid, the derivative of saturated acid such as acetate or propionic acid also is fit to.
Described titanium or zirconium compounds preferably contain at least two groups derived from unsaturated alcohol.
Just as mentioned before, the appropriate methodology of the described titanium compound of preparation or zirconium compounds is the reaction of four alcoxylates of unsaturated alcohol and titanium or zirconium.For example, pentenol is joined in the tetraisopropoxy titanium then and to remove the Virahol that replaces by distillation and prepare and be used for compound of the present invention.Can regulate the mole of pentenol and tetraisopropoxy titanium and recently prepare a series of compounds, comprise four amylene oxygen base titaniums or amylene oxygen base, isopropoxy titanium compound.
In general, when in described titanium or zirconium compounds, having the group of non-alkenyloxy or non-chain alkoxy, be easy to carry out by the four alkenyloxy compounds of as above preparation and the described compound of prepared in reaction of other reagent.For example 1 mole of glycol ether is joined then to remove pentenol in 1 mole of four amylene oxygen base titanium and prepare and be used for glycol ether compound of the present invention.
In general, any polymerisable compound that is used for preparing the printing ink of radiation-hardenable all can be present in printing ink of the present invention.Described polymerisable compound must contain at least a monomer, but also often contains the oligopolymer that is called " prepolymer " usually.
Usually, these prepolymers contain acrylic-functional, and suitable prepolymer comprises epoxy acrylate.Acrylate carburetion, urethane acrylate, polyester acrylate, polyether acrylate, vinyl/acrylic acid oligomer, unsaturated polyester and polyenoid/mercaptan system.Still in general described acrylic-functional (when existing) can, be preferred based on acrylic acid polymerisable compound from the vinylformic acid such as the methacrylic acid of vinylformic acid or replacement.
Described unsaturated monomer is selected from a large amount of possible monomer or monomer components, can be simple function or polyfunctional.The monofunctional monomer that is fit to comprises vinylbenzene, vinyl methyl, vinyl-acetic ester, N-vinyl pyrrolidone and acrylate or methacrylic ester such as butyl acrylate, butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, vinylformic acid 2-diethyl acetamidomalonate, methacrylic ester 2-ethylhexyl and isodecyl acrylate.The polyfunctional monomer that is fit to comprises that the acrylate of polyvalent alcohol is such as glycol diacrylate.Diethylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, Viscoat 295 and tetramethylol methane tetraacrylate.
Usually, described monomer contains the polymerisable compound of 20% (weight) at least.
Described printing ink contains a kind of pigment or dyestuff.The pigment or the dyestuff of any routine all are suitable for, and it is selected by the required color decision of printing ink.Mineral dye all is fit to as pthalocyanine blue with pigment dyestuff with silicate as carbonate as titanium pigment, zirconium pigment, chrome pigment and filler.If do not disturb the polymerization of described polymerizable thing when using, can comprise ultraviolet reactive dyestuffs when needing so yet.
In the use, printing ink of the present invention is printed on the substrate and by being exposed to for example ultraviolet ray (UV) radiation or electron beam and solidifies down.
Being exposed to the curing of UV radiating uses mercury vapor lamp or xenon lamp to carry out usually.Preferred UV source of radiation is the middle pressure mercury vapor lamp of working under the situation with lineal measure 40-300 watt power output of every centimetre of lamp.General power is output as lineal measure 60-150 watt of every centimetre of lamp.Be effective curing, the linear speed that is generally per second 5-120 centimetre is passed through described printing-ink under this lamp, and usually under this lamp by 2-4 time to carry out completely solidified.
In general, when printing ink during, initiator is joined in the printing ink to improve solidification rate through the UV radiation curing.The light trigger that is fit to comprises bitter almond oil camphor; benzene idol cigarette butyl ether; the benzil ketone acetal; the derivative of phenyl methyl ketone is as 2; 2-diethoxy phenyl methyl ketone, α, α-two chloracetyl is to phenoxy group benzophenone and 1-hydroxy-cyclohexyl phenyl methyl ketone and benzophenone and derivative such as chlorobenzene and benzophenone, acroleic acid esterification benzophenone, 4-phenyl benzophenone and 4-benzoyl-4-methyldiphenyl base sulphur.
When solidifying described printing ink, use the instrument of under 150-500KeV, operating usually with returning of electron beam method.The exposure of described printing ink under electron beam is by the thickness decision according to the print film of parameter known in the art.Controlling electron beam stream is enough to produce completely crued energy to guarantee to receive at rete/substrate rete at the interface.
Described printing ink is particularly suitable for being used on compound oriented polypropylene, polypropylene and the poly terephthalic acid binaryglycol ester, is good to the binding property of these substrates.
The present invention is illustrated in the following example.
Embodiment 1
344g 2-methyl-3-butene-2-alcohol slowly joined from funnel agitator, condenser and dropping funnel are housed and contain the round-bottomed flask of 284g tetra isopropyl titanate.Stir content and finish until reaction, underpressure distillation is removed the Virahol that disengages and is obtained mobile transparent liquid.
Reaction product above 1.9 weight parts is joined 100 weight parts by K﹠amp; The blue look of the Ultraking by name 1 blue printing ink that E PrintingInks sells is in the printing ink of UV-curable.
Then this printing ink is applied on the oriented polypropylene band and uses laboratory scale UV curing room to solidify.The film that is printed is with following 5 times of the speed of 15 centimetres of the per seconds LV lamp by every centimetre of lamp line one length 79.Except used printing ink does not have described additive, prepare the second polypropylene tape in the same way.
To every polypropylene tape, guarantee well contact with enough pressure applying adhesive tape that 2.5cm is wide.In a word, very fast adhesive tape is taken off, sticked and take off fast at same place again.The visual inspection result of described polyene bar shows that the printing ink that does not have or do not contain described additive substantially is removed, otherwise about 50% unmodified printing ink is removed.
Embodiment 2
Except the additive that 2.0 weight parts are formed by 440g four n-propyl zirconates and the pure reaction of 344g 3-methyl-2-butene-1-joined in the 100 weight part printing ink, other was identical with embodiment 1.
Obtain similar result with mensuration with embodiment 1 the same manner.
Embodiment 3
Except replacing 2-methyl-3-butene-2-alcohol, with method preparation four (3-methyl-2-butene-1-oxygen base) titanium of embodiment 1 with 3-methyl-2-butene-1-alcohol.Concentration with 3% (weight) joins this product in the printing ink with following prescription.The zirconium compounds of the embodiment 2 of 3% (weight) also is added in this printing ink.
Formulation weight part
Blue look pigment (Irgalite Bule GLO)
(1)12
Epoxide/origoester acrylate (Craynor 104D80)
(2)98
The Viscoat 295 of ethoxylation (Sartomer454)
(2)30
1,6 hexanediol diacrylate (Sartomer238)
(2)58
Amine origoester acrylate (Craynor386)
(2)12
Promotor (Irgacor L184)
(1)6
Light trigger (benzophenone) 8
Light trigger (Darocur 1173)
(1)2
(1) available from Cibe-Geigy
(2) available from Cray Valley Products
These component ball millings mixing are spent the night.
This printing ink is used, solidified and measure as described in the embodiment 1.After taking adhesive tape off, about 20% does not have the printing ink of additive to remain on the described film, and about 95% printing ink and 100% printing ink that contains the additive of embodiment 2 that contains the additive of embodiment 3 is kept.
Embodiment 4
By each component ball milling is had the ink formulations of following composition after preparation yesterday:
Formulation weight part
Blue look pigment (Irgalite Bule GLO)
(1)12
Epoxide/origoester acrylate (Craynor 104D80)
(2)98
The Viscoat 295 of ethoxylation (Sartomer454)
(2)30
1,6 hexanediol diacrylate (Sartomer238)
(2)58
Promotor (Irgacor L184)
(1)6
Light trigger (Darocur 1173)
(1)2
Light trigger (benzophenone) 8
Trolamine 6
(1) available from Cibe-Geigy
(2) available from Cray Valley Products
The product of embodiment 2 ratio with 3% (weight) is joined in a part of this printing ink.Printing ink is measured as embodiment 1.After peelling off adhesive tape, about 30% does not have the printing ink of additive to stay on the described film, and the printing ink that contains described additive is then had an appointment and 80% obtained keeping.
Claims (15)
1. the printing ink of radiation curing that contains the mixture of polymerisable compound, pigment or dyestuff, described polymerisable compound comprises at least a unsaturated monomer and optional at least a prepolymer, and can polymerization is characterized in that a kind of titanium compound or zirconium compounds of alkoxy compound of unsaturated alcohol is present in the described mixture by being exposed to radiation.
2. according to the printing ink of claim 1, it is characterized in that described unsaturated alcohol is a kind of alkenols that contains 8 carbon atoms at most.
3. according to the printing ink of claim 1, it is characterized in that the alcoxylates of described unsaturated alcohol has general formula (RO)
4X, R is the alkenyl of alkenyl or replacement in the formula, X is titanium or zirconium.
4. according to the printing ink of claim 1, the alcoxylates that it is characterized in that described unsaturated alcohol is alkoxyl group, alkenyloxy compound or based on the chelating ligand of alkanolamine, beta-diketon or glycol, or the derivative of a kind of glycol ether, polyoxyethylene glycol, vinylformic acid, methacrylic acid, acetate or propionic acid.
5. according to the printing ink of claim 1, it is characterized in that the alcoxylates of described unsaturated alcohol contains at least two groups from unsaturated alcohol.
6. according to the printing ink of claim 1, it is characterized in that described polymeric composition comprises a kind of oligopolymer, this oligopolymer is epoxy acrylate, acrylate carburetion, urethane acrylate, polyester acrylate, polyether acrylate, vinyl/acrylic acid oligomer, unsaturated polyester or polyenoid/mercaptan system.
7. according to the printing ink of claim 1, it is characterized in that described unsaturated monomer is vinylbenzene, Vinyl toluene, vinyl-acetic ester, N-vinyl pyrrolidone, butyl acrylate, butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-EHA, methacrylic acid 2-ethylhexyl, isodecyl acrylate, glycol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, Viscoat 295 or tetramethylol methane tetraacrylate.
8. according to the printing ink of claim 1, it is characterized in that described unsaturated monomer comprises the polymerisable compound of at least 20% (weight).
9. according to the printing ink of claim 1, it is characterized in that described dyestuff is a kind of ultraviolet reactive dyestuffs.
10. printing process, it comprises the ink printing of mixture of polymerisable compound, pigment or dyestuff to substrate and by being exposed under the radiation described ink solidification, described polymerisable compound comprises at least a unsaturated monomer and optional at least a prepolymer, it is characterized in that the titanium or the zirconium compounds of the alcoxylates of unsaturated alcohol is present in the described mixture.
11., it is characterized in that the solidified by ultraviolet ray radiation of described printing ink by providing by middle pressure mercury vapor lamp with 40-300 watt of power output services of every centimetre of linear modulation length according to the printing process of claim 11.
12., it is characterized in that the printing ink of described printing passes through under described lamp with per second 5-120 centimetre linear velocity according to the printing process of claim 11.
13. according to the printing process of claim 11, it is characterized in that described printing-ink under described lamp by 2-4 time to reach completely solidified.
14. printing process according to claim 10, it is characterized in that described printing ink passes through solidified by ultraviolet ray radiation, and initiator is added in the printing ink, and described initiator is the derivative of bitter almond oil camphor, bitter almond oil camphor butyl ether, benzil ketone acetal, phenylacetyl or the derivative of benzophenone.
15。According to the printing process of claim 10, wherein said printing ink is used in the 150-500KeV electron beam instrument curing of work down.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96111639 CN1156160A (en) | 1995-08-05 | 1996-08-02 | Ink |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9516108.9 | 1995-08-05 | ||
| CN 96111639 CN1156160A (en) | 1995-08-05 | 1996-08-02 | Ink |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1156160A true CN1156160A (en) | 1997-08-06 |
Family
ID=5121212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96111639 Pending CN1156160A (en) | 1995-08-05 | 1996-08-02 | Ink |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1156160A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443308C (en) * | 2002-12-20 | 2008-12-17 | 塞里考尔有限公司 | Curing |
| CN102182081A (en) * | 2011-03-15 | 2011-09-14 | 珠海保税区天然宝杰数码科技材料有限公司 | Ink-jet printing pigment ink and ink-jet printing method |
-
1996
- 1996-08-02 CN CN 96111639 patent/CN1156160A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443308C (en) * | 2002-12-20 | 2008-12-17 | 塞里考尔有限公司 | Curing |
| CN102182081A (en) * | 2011-03-15 | 2011-09-14 | 珠海保税区天然宝杰数码科技材料有限公司 | Ink-jet printing pigment ink and ink-jet printing method |
| CN102182081B (en) * | 2011-03-15 | 2012-09-19 | 珠海保税区天然宝杰数码科技材料有限公司 | Ink-jet printing pigment ink and ink-jet printing method |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |