CN1961051A - Photoinitiators for use in intaglio printing inks - Google Patents
Photoinitiators for use in intaglio printing inks Download PDFInfo
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- CN1961051A CN1961051A CNA2005800179167A CN200580017916A CN1961051A CN 1961051 A CN1961051 A CN 1961051A CN A2005800179167 A CNA2005800179167 A CN A2005800179167A CN 200580017916 A CN200580017916 A CN 200580017916A CN 1961051 A CN1961051 A CN 1961051A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
An intaglio printing ink, curing by free radical acrylate chemistry, which does not fluoresce in at least the visible region under ultraviolet light is prepared by using an acylphosphine oxide as the photoinitiator.
Description
But the present invention relates in energy-curable (but for example ultraviolet curing) gravure printing ink some acylphosphine oxide as the purposes of photoinitiator.
Secure file is preferably by the gravure process printing.The employed term of the application " intaglio printing " refers to so-called " engraving punching block " or " copperplate " printing process, and they are that those skilled in the art is known.Forme used herein is normally chromed, engraving nickel version or cylinder, is to be duplicated and made by the plating of hand engraving copperplate.Following inapplicable rotogravure printing method or the gravure process of knowing equally of content, they rely on dissimilar printing ink.
In intaglio printing, printing ink is applied to the sculpture surface of cylinder under pressure.Therefore, printing ink has not only been filled the depiction of cylinder, and it also is applied to the non-pattern flat surfaces of cylinder.Then, before carrying out printing process, printing ink is wiped fully from the flat surfaces of engraved roll.This generally realizes by the wiping cylinder with respect to the engraved roll reverse rotation, makes contacted two surfaces move in the opposite direction.Suppose under appropriate condition, and it is highly important that under the situation of suitable printing ink, this will remove unnecessary printing ink from flat surfaces, simultaneously also the ink pellet surface from depiction being removed a small amount of printing ink, is in depiction at only printing ink on the engraved roll therefore.Then, stock to be printed passes through between engraved roll and impression materials, and described impression materials generally is another cylinder, applies sizable pressure between engraved roll and impression materials, and this impression materials is hard and deformable material.This sizable pressure makes impression materials distortion, forces stock to be printed in the depiction on the engraved roll.This causes stock to obtain some printing ink, corresponding to the lip-deep depiction of engraved roll.Then, printing ink must carry out drying.
Because the specific characteristic of intaglio printing is used for other mode of printing such as lithographic printing ink, can not be used to intaglio printing, and prescription is often different fully.
Clearly, the rheology of printing ink successfully is crucial to it.For the oil base gravure printing ink, the adding of organic solvent allows rheol adjustment, has promoted the wiping of superfluous printing ink from the non-pattern area of forme simultaneously.But this kind solvent is not used in the energy curable inks, but therefore described energy curable inks is more tacky, and needs to use softening agent to obtain same effect.
Except rheology discussed above and the easy removal of superfluous printing ink, gravure printing ink also must satisfy following requirement:
They must remain on the engraved roll, and till printing constantly, this moment, they must be easily and be transferred to stock to be printed in the mode of unanimity.
They must have good film forming properties, and curing inks must be fully flexible, even so that when being printed material (for example banknote) when being abused, they still are kept perfectly harmless.
In case stock is printed, printing ink must not transfer printing be got back to other surface that it may contact, and particularly other is printed thing.
Curing inks must have splendid chemical resistant properties and mechanical resistance, so that withstand a lot of different material and condition that banknote may run into.
They must be safe to all public members' of comprising very young people touch.
At printing ink is by the energy situation of ultraviolet ray or electrocuring for example, is added in the printing ink and must disturb curing with any component that realizes above-mentioned any requirement, and this also is self evident.Not surprisingly, be not difficult to satisfy simultaneously all these expectations.
The most of gravure printing inks that use are printed on the sheet-fed press at present.Main drying mechanism is that this is one needs a couple of days usually so that the process of finishing substantially by the resin in the layer of printed matter and the oxidation of oil ingredient.This drying process has following shortcoming: wet ink may be transferred to not printing surface when making up layer, perhaps even the result that may move as any layer in the process that oxidation drying takes place and shifting.This type of ink transfer at industrial being called as " set-off ", and is considered to mistake to printing surface not usually.
Therefore, but proposed the energy solidified, particularly can ultraviolet ray (UV) solidified gravure printing ink.Use can connect the generation that the material system provides dry at once and eliminated set-off by solidified under the effect of UV-light.For example, GB 1466470 discloses the UV-curable ink that is used for the copperplate intaglio printing, and it comprises: the curable adhesive of specified quantitative, this tackiness agent are acrylic acid ester or acid amides; Pigment; Photoinitiator; The activator of this photoinitiator; And the inertia extender that can see through UV-light.EP1,260,563 disclose UV gravure printing ink prescription, and it can be washed, and at the wiping latter stage, it can easily precipitate from polishing solution.
Yet the main practical use of current intaglio printing is the security printing of banknote for example, and this generally requires employed printing ink should not fluoresce at visible region under UV-light.Especially, banknote generally is printed on the non-fluorescent paper, and therefore, the test first time of measuring banknote and whether be counterfeit money is to place it under the ultraviolet source.If banknote sends blue-fluorescence, then this banknote almost is counterfeit money certainly.At this background, printing press is selected ink application, described printing ink itself or fluoresce or do not fluoresce, perhaps even be two types combination.Therefore, in order to make full use of safe possibility, importantly printing ink manufactory has sufficient prescription elasticity, to produce fluorescence and non-fluorescent ink.Because being proposed for the photoinitiator of above-mentioned patent is combined under the UV-light and fluoresces really in the visible region, this has got rid of the production of non-fluorescent ink, therefore, its prescription can not be used to a large amount of application in practice, otherwise in these are used they to be expected to be useful.
We are surprised to find now, the acylphosphine oxide photoinitiator, and---it is the photosensitive initiator of free radical---do not fluoresce in visible region under UV-light, therefore can be used in the energy-curable intaglio printing inks, is used for Secure Application.
Known acylphosphine oxide can be used as the photoinitiator in various other type printing-inks.For example, US 6,777,459 B2 have described the purposes of the composition with single and two acylphosphine oxides, and described their suitabilities to ultraviolet curing ink, comprise silk screen printing, flexographic printing, intaglio printing and offset printing.US 4,710,523 and US 4,298,738 some acylphosphine oxides and they have been described as the purposes of photoinitiator in photopolymerization topcoating, finish paint and printing-ink.Yet they do not show that these compounds can be used to gravure printing ink, do not show that formed printing ink does not fluoresce in the visible region under UV-light yet.
Therefore; the present invention relates to energy-curable intaglio printing inks, it is by free radical acrylate chemistry solidified, and comprises photoinitiator; described photoinitiator comprises acylphosphine oxide, and wherein described printing ink does not fluoresce in visible wavelength district at least when being exposed to UV-light.
Spectrographic " visible region " is the normal visible of people zone, and general in 400 to 700nm scope.
The preferred compound of a class used in this invention is those compounds of formula (I):
Wherein:
R
1And R
2Be independently selected from C
1-C
12Alkyl; C
3-C
7Cycloalkyl; Aryl; Aralkyl; Heterocyclic group with 3 to 7 annular atomses, at least one is oxygen, sulphur or nitrogen-atoms in described annular atoms; And has formula-COR
3Group;
Perhaps R
2Representative has formula-OR
4Group, R wherein
4Represent C
1-C
6Alkyl, aryl, aralkyl or cation group or atom, perhaps R
2The group of representative formula (II):
Wherein X represents C
1-C
18Alkylidene group or biphenyl two bases, and R
5Represent arbitrary by R
1The group or the formula-OR of expression
4Group; With
R
3Represent C
1-C
6Alkyl; Aryl; Heterocyclic group with 3 to 7 annular atomses, at least one is oxygen, sulphur or nitrogen-atoms in described annular atoms; The perhaps group of formula (IV):
Wherein Y represents C
1-C
18Alkylidene group, phenylene, cyclohexylidene or biphenyl two bases.
In the compound of formula (I), R wherein
1And/or R
2Represent alkyl, it can be the straight or branched alkyl with 1 to 12 carbon atom.The example of this type of group comprises methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, hexyl, isohexyl, heptyl, octyl group, nonyl, decyl, undecyl and dodecyl.In these groups, especially preferably those have the group of 1 to 8 carbon atom for we, more preferably the group of 1 to 6 carbon atom.Most preferred group is those groups with 1 to 4 carbon atom.Work as R
3And/or R
4When representing alkyl, it can be the straight or branched group with 1 to 6 carbon atom, preferred 1 to 4 carbon atom, the example of this type of group comprise have this number carbon atom, those groups listed above.
Work as R
1And/or R
2During representation ring alkyl, it has 3 to 7 ring carbon atoms, and example comprises cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and suberyl, and in these groups, cyclopentyl and cyclohexyl are preferred.
Work as R
1And/or R
2And/or R
3And/or R
4When representing aryl, it is for preferably having the group of 6 to 14 carbon atoms on aromatic carbocyclic, and example comprises phenyl, naphthyl, anthryl and phenanthryl, and in these groups, phenyl is preferred.This type of group can be replacement or unsubstituted.If replace,, substituent number is had no particular limits except those numbers by the substitutable carbon atom and the substituting group that may force by space constraint, yet, generally speaking, 1 to 4 substituting group, more preferably 1 to 3 substituting group will be common.The example of suitable substituents comprises halogen atom (for example chlorine, fluorine, bromine or iodine atom), C
1-C
6Alkyl (for example is included in by R
1And/or R
2Those alkyl in the examples of alkyl groups of expression, that have 1 to 6 carbon atom), C
1-C
6Alkoxyl group, C
1-C
6Alkylthio and aryl (for example, example, and so place definition as shown here, it can be replacement or unsubstituted, condition is that any aryl substituent itself cannot further be replaced by aromatic yl group).
When the substituting group on the aryl (one or more) when being alkoxyl group, this can be the straight or branched group with 1 to 6 carbon atom, in these groups, example comprises methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy, pentyloxy, isopentyloxy, neopentyl oxygen and hexyloxy.
When the substituting group on the aryl (one or more) when being alkylthio, this can be the straight or branched group with 1 to 6 carbon atom, in these groups, example comprises methylthio group, ethylmercapto group, rosickyite base, iprotiazem base, butylthio, isobutyl sulfenyl, secondary butylthio, uncle's butylthio, penta sulfenyl, isoamyl sulfenyl, new penta sulfenyl and own sulfenyl.
Work as R
1And/or R
2And/or R
4When representing aralkyl, this can be an alkyl, preferably has 1 to 4 carbon atom, and it is replaced by 1 to 3 aryl, its can be as defined above with example.The preferred example of this type of aralkyl comprises benzyl, diphenyl-methyl, trityl, styroyl, 1-styroyl, 3-hydrocinnamyl, 4-benzene butyl and menaphthyl group, and in these groups, benzyl is preferred.
Work as R
1And/or R
2And/or R
3When representing heterocyclic group, it has 3 to 7 annular atomses, in these annular atomses, at least one, preferred 1 or 2, more preferably 1 is Sauerstoffatom, nitrogen-atoms or sulphur atom.More preferably, described group has 5 or 6 annular atomses, and in these annular atomses, a preferred annular atoms is oxygen, nitrogen or sulphur atom.The example of this type of group comprises thienyl, furyl, pyranyl, pyrryl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyrrolidyl, pyrrolinyl, imidazolidyl, imidazolinyl, piperidyl, piperazinyl and morpholinyl, in these groups, thienyl and pyridyl are preferred.
Work as R
4Represent cation group or atomic time, this for example can be an ammonium group, perhaps atoms metal (M)
+ x, wherein M is a metal, for example sodium, potassium or lithium, and x is valent inverse of metal M.
When X or Y represent alkylidene group, this can be the straight or branched group with 1 to 18 carbon atom, and example comprises methylene radical, ethylidene, 1,3-propylidene, propylidene, tetramethylene, 1,5-pentylidene, hexamethylene, 1, the inferior heptyl, 1 of 7-, 8-is octylene, nonamethylene, decamethylene, undecane support, 12 methylenes, tridecane support, tetradecane support, pentadecane support, n-Hexadecane support, heptadecane support and octadecane support group.
Those compounds that to be used in the particularly preferred class acylphosphine oxide among the present invention be formula V:
Wherein:
R
1Represent C
1-C
12Alkyl, cyclohexyl or aryl; With
R
3As above definition.
The compound of our preferred especially formula V, wherein each R
3Be independently selected from phenyl and have 1 to 4 halogenic substituent and/or C
1-C
6Alkyl substituent and/or C
1-C
6The phenyl of alkoxy substituent.
The equally preferably compound of formula V, wherein R
1Represent C
1-C
12Alkyl or phenyl, described phenyl is unsubstituted, perhaps has 1 to 3 C
1-C
6Alkyl or alkoxy substituent.
The particularly preferred another kind of acylphosphine oxide that is used among the present invention is those compounds of formula (VI):
Wherein:
R
1And R
3As above definition; With
R
2aRepresent C
1-C
12Alkyl; C
3-C
7Cycloalkyl; Aryl; Aralkyl; Heterocyclic radical with 3 to 7 annular atomses, in these annular atomses, at least one is oxygen, sulphur or nitrogen-atoms; Perhaps R
2aRepresent Shi-OR
4Group, R wherein
4Definition as above.
Most preferred classification of the present invention is those compounds of formula (VII):
Wherein:
N is 0 or 1;
R
6Represent C
1-C
12Alkyl, C
1-C
6Alkoxyl group, phenyl or have 1 to 4 substituent phenyl, described substituting group is selected from C
1-C
6Alkyl, C
1-C
6Alkoxyl group and halogen atom; With
R
7, R
8, R
9, R
10, R
11And R
12Be identical or different each other, and each represent hydrogen atom, C
1-C
6Alkyl, C
1-C
6Alkoxyl group or halogen atom.
Object lesson that can photoinitiator used in this invention comprises: methyl 2; 6-dimethylbenzoyl-Phenylphosphine acid esters; methyl 2; 6-dimethoxy benzoyl-Phenylphosphine acid esters; 2; 6-dimethylbenzoyl diphenyl phosphine oxide; 2; 6-dimethoxy benzoyl diphenyl phosphine oxide; methyl 2; 4; 6-trimethylbenzoyl-Phenylphosphine acid esters; ethyl 2; 4; 6-trimethylbenzoyl-Phenylphosphine acid esters; (2; 4; the 6-trimethylbenzoyl)-(2 '-Hydroxybiphenyl-2-yl) phosphonic acids potassium; 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; 2; 4; 6-trimethoxy benzoyl diphenyl phosphine oxide; 2; 3; 6-trimethylbenzoyl diphenyl phosphine oxide; methyl 2; 4; 6-trimethylbenzoyl-tolylphosphine acid esters; ethyl 2; 6-dichloro-benzoyl base-Phenylphosphine acid esters; 2; 6-dichloro-benzoyl base diphenyl phosphine oxide; 2; 6-dibromobenzene formyl radical diphenyl phosphine oxide; 2-chloro-6-methyl thiobenzoyl diphenyl phosphine oxide; 2; 6-dimethyl thiobenzoyl diphenyl phosphine oxide; 2; 3; 4; 6-tetramethyl-benzene formyl radical diphenyl phosphine oxide; 2-phenyl-6-methyl benzoyl diphenyl phosphine oxide; methyl 2; 4; 6-trimethylbenzoyl-naphthyl phosphonic acid ester; ethyl 2; 4; 6-trimethylbenzoyl-naphthyl phosphonic acid ester; ethyl 2; 6-dichloro-benzoyl base-naphthyl phosphonic acid ester; 1; 3-dimethylnaphthalene-2-carbonyl-diphenyl phosphine oxide; 1; 3-dimethoxy-naphthalene-2-carbonyl-diphenyl phosphine oxide; 1; 3-dichloronaphtalene-2-carbonyl-diphenyl phosphine oxide; 2; 8-dimethylnaphthalene-2-carbonyl-diphenyl phosphine oxide; 2; 4; 6-trimethylpyridine-3-carbonyl diurethane phenyl phosphine oxide; 2; 4-dimethyl furan-3-carbonyl diurethane phenyl phosphine oxide; 2; 4-dimethoxy furans-3-carbonyl diurethane phenyl phosphine oxide; methyl 2; 4; 5-trimethylthiophene-3-carbonyl diurethane phenyl phosphine oxide; 2; 4,5-trimethylthiophene-3-carbonyl diurethane phenyl phosphine oxide; two (2,6-dimethoxy benzoyl)-2; 4; 4-tri-methyl-amyl-phosphine oxide and two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide.
Also can use other acylphosphine oxide photoinitiator, for example 1, two [two (2,4, the 6-trimethylbenzoyl) phosphine oxide] decane and the 4-acryloxies-2 of 10-, the multipolymer of 6-dimethylbenzoyl-diphenyl phosphine oxide and butyl acrylate.
Most preferred acylphosphine oxide is 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4; the 6-trimethylbenzoyl) phenyl phosphine oxide, ethyl 2,4,6-trimethylbenzoyl diphenylphosphine acid esters and two (2; 6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide.
These acylphosphine oxides itself all are known, and can be by known method or by preparing with the similar method of these currently known methodss.For example, they are at United States Patent (USP) the 4th, 298, and 738,4,710,523 and 6,777, to be described in No. 459, these disclosures are incorporated herein by reference.
Although it is feature of the present invention that photoinitiator comprises acylphosphine oxide, if expectation can re-use other photoinitiator in addition, condition is that they can not be created under the UV-light fluorescigenic curing inks in the visible region yet.For example, might use the free radical/cationic curing system and the suitable cationic initiator of hydridization, wherein the photosensitive initiator of free radical is an acylphosphine oxide of the present invention.
Printing-ink of the present invention is designed to by ultraviolet ray or EB (electron beam) radiation curing, and typically comprises tackiness agent, and described tackiness agent comprises one or more oligopolymer and/or reactive monomer.Prescription is known, and can find in standard textbook, for example, and by John Wiley ﹠amp; Book series " the Chemistry ﹠amp that amounts to 7 volumes that Sons and SITA Technology Limited publish in 1997-1998; Technology of UV ﹠amp; EB Formulation for Coatings, Inks ﹠amp; Paints ".
Suitable oligopolymer (being also referred to as prepolymer) comprises oil, urethane acrylate, polyester acrylate, the siloxanes acrylate of epoxy acrylate, acrylated, amine, vinylformic acid saturated resin and the acrylic acrylate of acrylated.At John Wiley ﹠amp; " the Chemistry ﹠amp that Sons and SITA TechnologyLimited edit in 1997 publication, G Webster; Technology of UV ﹠amp; EB Formulation for Coatings, Inks ﹠amp; Paints ", Volume II:Prepolymers ﹠amp; More details and example are provided among the Reactive Diluents.
Because most of oligopolymer has high viscosity,,, handle and use so that help to reduce total viscosity of energy curable inks or coating formula so need thinner.Suitable diluent can comprise water or " activity " monomer, and they are introduced in the solidified film.Reactive monomer is generally acrylate or methacrylic ester, and can be simple function or polyfunctional.The example of polyfunctional monomer comprises polyester acrylate or methacrylic ester, polyalcohol acrylate or methacrylic ester and polyether acrylate or methacrylic ester.More details and example provide in the book of being edited by G Webster (quoting as preceding institute).
In order to make printing ink be fit to water wiping gravure printing machine, printing ink must be soluble in the caustic solution of dilution.This can realize by using sour functional resin.These can be that acrylate or methacrylic ester are functional, are active or inert in ultraviolet ray and e-beam system therefore.Suitable example comprises the styrene-maleic anhydride resin, for example supplies SMA1440F and aromatic acid methacrylic ester and acrylate half ester from Cray Valley.
Printing ink will contain pigment as tinting material.Pigment can be any desired inorganic and/or pigment dyestuff that is fit to intaglio printing, for example CI pigment Yellow 12, CI Pigment Yellow 73 42, CI Pigment Yellow 73 93, CI Pigment Yellow 73 110, CI pigment yellow 17 3, CI Pigment black 7, CI Pigment black 11, CI pigment orange 34, the CI Pigment Red 9, CI Pigment red 22, CI Pigment red 23, CI Pigment red 57:1, CI Pigment red 67, the CI pigment red 122, the CI pigment red 146, CI Pigment red 185, CI Pigment red 224, CI Pigment red 242, CI Pigment red 254, the CI pigment Green 7, the CI pigment green 36, the CI pigment Blue 15, CI pigment Blue 15: 3, the CI pigment Violet 23, CI pigment violet 32 or CI pigment violet 37.
Preferably, printing ink will contain one or more fillers (also being known as extender), and its content is about 1-35% based on the weight of finished product printing ink.Appropriate filler comprises potter's clay, lime carbonate, calcium sulfate, talcum, silica, W-Gum, titanium dioxide, aluminum oxide and composition thereof.
The weight that printing ink also can contain based on finished product printing ink is about wax of 1 to 5%, to improve wearability.Suitable wax comprises carnauba wax, montanin wax, tetrafluoroethylene wax, polyethylene wax, Fischer-Tropsch wax, silicone fluid and composition thereof.
Other additive can be introduced in the printing ink, comprises tackiness agent, antifoams, levelling agent, flowing agent, antioxidant, UV light absorber, fire retardant etc.
In addition, if expectation, softening agent can be introduced in the printing-ink, and purpose is to promote wiping process, so that remove superfluous printing ink from engraved roll.The example of suitable manufacturing methods comprises:
Citrate, for example: citric acid acetyl three (2-second hexyl) ester, acetyl tributyl citrate, Triethyl citrate acetate, tributyl citrate, citric acid three cyclohexyls, triethyl citrate and citric acid three isopentyl ester;
Epoxidized oil, lipid acid and ester thereof, for example: the 2-ethylhexyl of epoxidation tallol, epoxidised linseed oil, epoxidised soybean fatty acid ethylhexyl, epoxidized soybean oil;
Lipid acid, it can be saturated or undersaturated, particularly those have those lipid acid of the molecular weight in the top given preferable range, caproic acid for example, sad, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid, mountain Yu acid, tetracosanoic acid, lauroleic acid (lauroleic acid), pentadecylic acid, margaric acid, Oleomyristic acid, Zoomeric acid, oleic acid, cis-9-20 carbon acid (eicosenoic acid), erucic acid, ricinolic acid, linolic acid, linolenic acid, licanic acid, eleostearic acid (Linolenic Acid, 11, the 13-trienic acid), therapic acid and punicic acid;
The mixture that the composition of these lipid acid, particularly occurring in nature are found, for example Semen Lini oil lipid acid or tall oil fatty acid;
Sebate, for example: sebacic acid 1,2-propylene glycol polyester, Diisooctyl Sebacate, Uniflex DBS and dioctyl sebacate;
The tallol ester, for example: the own ester of resinous acid, resinous acid 2-ethylhexyl, isooctyl tallate and resinous acid octyl group epoxy ester;
Softening agent or wiping auxiliary agent preferably are introduced in the printing ink with 0.5% to 10% level, and more preferably 3 to 5%, this is to calculate by the weight of finished product printing ink.
In order suitably to play a role as gravure printing ink, the viscosity of printing ink should preferably be controlled in some boundary.Particularly, we are preferred, at 26 ℃ and 100sec
-1Shearing rate under the ink viscosity measured preferably in the scope of 20-200 pascal second, 50-125 pascal second more preferably.
The present invention also provides the method for producing file, described method comprises the use gravure printing ink, intaglio printing on stock, described stock do not fluoresce in visible region at least under UV-light, and described gravure printing ink comprises the photoinitiator that contains acylphosphine oxide; With solidify this printing ink by being exposed to radiation energy.
Stock is preferably paper.
Method of the present invention is particularly suitable for the printing of secure file such as banknote.In this case, paper or other stock will be selected as those materials of this class file from known.
Printing ink of the present invention can be used in that to be equipped with UV-lamp and forme temperature be on the about 40 ℃ standard concave printing machine.
The present invention is further explained by following indefiniteness embodiment.
Embodiment 1 and 2 and comparing embodiment 1
The composition shown in the following table 1 of weighing, and mix to form and stick with paste.Should stick with paste thorough mixing then, and use three roller runner millings that it is disperseed, to produce uniform viscosity paste-like ink, mixture A.
Table 1
| Material | Content (wt%) | Supplier |
| Ebecryl 648 (epoxy acrylate) | 51.3 | UCB chemicals |
| Tripropylene glycol diacrylate (TPGDA) | 1.1 | Cray Valley |
| Chromophtal LGLD (blue pigments) | 6.8 | Ciba |
| Deposit C aCO 3 | 33.4 | Omya |
| W-Gum | 2.5 | Cerestar |
| Carnauba wax | 3.7 | Eggar |
| Florstab UV-1 (UV stablizer) | 1.2 | Kromachem |
| Amount to | 100 |
Be dissolved in 50: 50 solution of Ebecryl 648 and TPGDA preparation photo sensitized initiation agent solution with 33% concentration by testing photoinitiator.By mixing, these solution are mixed with mixture A then,, be used for test to produce finished product printing ink with cutter.Use carved gravure, adopt the HarryRochat press printing printing ink of working out a draft, and to solidifying and the amount of fluorescence is analyzed.Be actual purpose, excite the fluorescence of printing ink down must be less than by paper institute emitted fluorescence at 364nm and 254nm.Can be under the light of these wavelength places emission visual assessment fluorescence, perhaps by use the UV spectrophotometer for example Perkin Elmer LS50 estimate fluorescence.Use is from the medium pressure mercury lamp curing inks of the 300W/ inch doping Ga of Fusion UV.
By being to scatter 10T hydraulic pressure on the disk of 3cm at diameter, a slice paper is touched on the solidified printing ink evaluate cure.
The photoinitiator of being estimated is listed in the following table 2, and this table also shows finished product oil film prescription and the result who estimates.
| Embodiment | Photoinitiator | Mixture A | PI％ | 50∶50 Ebecryl 648 ∶TPGDA | Rahn RCX-02-766 amine synergistic agent | Supplier | Fluorescence (254nm excites) | Fluorescence (365nm excites) | Solidify * |
| Comparing embodiment 1 | Esacure ITX | 81.3 | 3.3 | 12.9 | 2.5 | Lamberti | Be (bright orchid) | Be (bright orchid) | -1 |
| 1 | Lucerin TPO | 81.3 | 3.3 | 15.4 | - | BASF | Not | Not | +1 |
| 2 | Irgacure 819 | 81.3 | 3.3 | 15.4 | - | CIBA | Not | Not | +2 |
| Comparing embodiment 2 | Benzophenone | 81.3 | 3.3 | 12.9 | 2.5 | IGM Resins | Be (dark green) | Be (dark green) | -2 |
| Comparing embodiment 3 | Igracure 369 | 81.3 | 3.3 | 15.4 | - | Ciba | Be | Be | -2 |
| Comparing embodiment 4 | 2-ethyl thioxanthone | 81.3 | 3.3 | 12.9 | 2.5 | Lambson | Be | Be | -2 |
| Comparing embodiment 5 | Photoinitiator combination 1 | 81.3 | 6.3 | 12.4 | - | - | Be | Be | +1 |
| Comparing embodiment 6 | Photoinitiator combination 2 | 81.3 | 5.4 | 13.3 | - | - | Be | Be | +2 |
| Comparing embodiment 7 | Omnipol TX | 81.3 | 3.3 | 12.9 | 2.5 | IGM Resins | Be | Be | -1 |
*-2 very poor to+2 fine
is according to acylphosphine oxide of the present invention
ITX is the 2-isopropyl thioxanthone
Igracure 369 be 2 benzyls-2-dimethylin-4 '-the morpholino butyrophenone
Irgacure 819 is two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxides
Lucerin TPO is (2,4, the 6-trimethylbenzoyl) diphenyl phosphine oxide
Omnipol TX is poly-(oxygen-1,4-fourth two bases), α-[[(9-oxygen-9H-thioxanthene base) oxo] ethanoyl]-ω-[[[(9-oxygen-9H-thioxanthene base) oxo] ethanoyl] oxo]
Photoinitiator combination 1
| Photoinitiator | ％ |
| Esacure ITX | 50.00 |
| Lucerin TPO | 15.00 |
| Irgacure 369 | 35.00 |
Photoinitiator combination 2
| Photoinitiator | ％ |
| Esacure ITX | 55.6 |
| Irgacure 819 | 44.4 |
Embodiment 3
Water wiping printing ink
Use the Silverson high speed agitator, first three the kind component was in the following Table 3 mixed about 30 minutes, up to producing limpid amber varnish.Then other components are added in this mixture, and mix to form and stick with paste.Should stick with paste thorough mixing then, and use three-roll grinder to disperse, to produce uniform pasty state water wiping printing ink.
Table 3
| Material | Content (wt%) | Supplier |
| Ebecryl 657 | 30 | UCB chemicals |
| SMA1440F | 10 | Cray Valley |
| Sartomer SR494 | 17 | Cray Valley |
| Microtalc | 20.1 | Omya |
| Irgalite Blue LGLD | 5 | Ciba Geigy |
| Irgacure 819 | 4.9 | Ciba Geigy |
| Carnauba wax | 3 | Eggar |
| Florstab UV 1 | 1 | Kromachem |
| The tall oil fatty acid | 9 | Various |
Viscosity data is shown in the following table 4.
Table 4
| Shearing rate l/s | 2 | 100 |
| Viscosity Pas at 26 ℃ | 170.1 | 50.9 |
Embodiment 4
Water wiping printing ink
Use the Silverson high speed agitator, first three the kind component shown in mixed about 30 minutes in the following Table 5, up to producing limpid amber varnish.Then other components are added in this mixture, and mix to form and stick with paste.Should stick with paste thorough mixing then, and use three-roll grinder to disperse, to produce uniform pasty state water wiping printing ink.
Table 5
| Material | Content (wt%) | Supplier |
| Ebecryl 657 | 30 | UCB chemicals |
| SMA1440F | 10 | Cray Valley |
| Sartomer SR494 | 17 | Cray Valley |
| Microtalc | 20.1 | Omya |
| Irgalite Blue LGLD | 5 | Ciba Geigy |
| Lucirin TPO | 4.9 | Ciba Geigy |
| Carnauba wax | 3 | Eggar |
| Florstab UV 1 | 1 | Kromachem |
| The tall oil fatty acid | 9 | Various |
Viscosity data is shown in the following table 6.
Table 6
| Shearing rate l/s | 2 | 100 |
| Viscosity Pas at 26 ℃ | 190.4 | 52.4 |
Embodiment 5
Paper wiping printing ink
All components is in the following Table 7 added together, and mix to form and stick with paste.Should stick with paste thorough mixing then, and use three-roll grinder to disperse, to produce uniform pasty state paper wiping printing ink.
Table 7
| CN104 | 38.5 | Cray Valley |
| Sartomer SR494 | 19.5 | Cray Valley |
| Microtalc | 22.6 | Omya |
| Irgalite Blue LGLD | 5.5 | Ciba Geigy |
| Lucirin TPO | 2.4 | Ciba Geigy |
| Irgacure 819 | 2.5 | Ciba Geigy |
| Carnauba wax | 3 | Shamrock |
| Florstab UV 1 | 1 | Kromachem |
| The tall oil fatty acid | 5 | Various |
Viscosity data is shown in the following table 8.
Table 8
| Shearing rate l/s | 2 | 100 |
| Viscosity Pas at 26 ℃ | 653.1 | 54.5 |
Claims (21)
1. energy-curable intaglio printing inks by the chemosetting of free radical acroleic acid esterification, and comprises the photoinitiator that contains acylphosphine oxide, and wherein said printing ink does not fluoresce in visible wavelength district at least when being exposed to UV-light.
2. printing-ink according to claim 1, wherein said acylphosphine oxide are the compounds of formula (I):
Wherein:
R
1And R
2Be independently selected from C
1-C
12Alkyl; C
3-C
7Cycloalkyl; Aryl; Aralkyl; Heterocyclic group with 3 to 7 annular atomses, at least one is sulphur or nitrogen-atoms in described annular atoms; And has formula-COR
3Group;
Perhaps R
2Representative has formula-OR
4Group, R wherein
4Represent C
1-C
6Alkyl, aryl, aralkyl or cation group or atom, perhaps R
2The group of representative formula (II):
Wherein X represents C
1-C
18Alkylidene group or biphenyl two bases, and R
5Represent arbitrary by R
1The group or the formula-OR of expression
4Group; And R
3Represent C
1-C
6Alkyl; Aryl; Heterocyclic group with 3 to 7 annular atomses, at least one is sulphur or nitrogen-atoms in described annular atoms; The perhaps group of formula (IV):
Wherein Y represents C
1-C
18Alkylidene group, phenylene, cyclohexylidene or biphenyl two bases.
3. printing-ink according to claim 2, wherein said acylphosphine oxide are the compounds of formula V:
Wherein:
R
1Represent C
1-C
12Alkyl, cyclohexyl or aryl; With
R
3Such as in claim 2 definition.
4. printing-ink according to claim 3, wherein each R
3Be independently selected from phenyl and have 1 to 4 halogenic substituent and/or C
1-C
6Alkyl substituent and/or C
1-C
6The phenyl of alkoxy substituent.
5. according to claim 3 or the described printing-ink of claim 4, wherein R
1Represent C
1-C
12Alkyl or phenyl, described phenyl are unsubstituted or have 1 to 3 C
1-C
6Alkyl or alkoxy substituent.
6. printing-ink according to claim 2, wherein said acylphosphine oxide are the compounds of formula (VI):
Wherein:
R
1And R
3Such as claim 2 definition; With
R
2aRepresent C
1-C
12Alkyl; C
3-C
7Cycloalkyl; Aryl; Aralkyl; Heterocyclic radical with 3 to 7 annular atomses, in these annular atomses, at least one is sulphur or nitrogen-atoms; Perhaps formula-OR
4Group, R wherein
4Such as claim 2 definition.
7. printing-ink according to claim 2, wherein said acylphosphine oxide are the compounds of formula (VII):
Wherein:
N is 0 or 1;
R
6Represent C
1-C
12Alkyl, C
1-C
6Alkoxyl group, phenyl or have 1 to 4 substituent phenyl, described substituting group is selected from C
1-C
6Alkyl, C
1-C
6Alkoxyl group and halogen atom; With
R
7, R
8, R
9, R
10, R
11And R
12Be identical or different each other, and each represent hydrogen atom, C
1-C
6Alkyl, C
1-C
6Alkoxyl group or halogen atom.
8. printing-ink according to claim 2; wherein said acylphosphine oxide is 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4; the 6-trimethylbenzoyl) phenyl phosphine oxide, ethyl 2; 4,6-trimethylbenzoyl diphenylphosphine acid esters or two (2,6-dimethoxy benzoyl)-2; 4,4-tri-methyl-amyl phosphine oxide.
9. method of producing file, described method comprises the use gravure printing ink, by the chemosetting of free radical acroleic acid esterification, intaglio printing on stock, described stock does not fluoresce in visible region at least under UV-light, and described gravure printing ink comprises the photoinitiator that contains acylphosphine oxide; With solidify this printing ink by being exposed to radiation energy.
10. method according to claim 9, wherein said radiating capacity are ultraviolet rays.
11. according to claim 9 or the described method of claim 10, wherein said acylphosphine oxide is the compound of formula (I):
Wherein:
R
1And R
2Be independently selected from C
1-C
12Alkyl; C
3-C
7Cycloalkyl; Aryl; Aralkyl; Heterocyclic group with 3 to 7 annular atomses, at least one is sulphur or nitrogen-atoms in described annular atoms; And has formula-COR
3Group; Perhaps R
2Representative has formula-OR
4Group, R wherein
4Represent C
1-C
6Alkyl, aryl, aralkyl or cation group or atom, perhaps R
2The group of representative formula (II):
Wherein X represents C
1-C
18Alkylidene group or biphenyl two bases, and R
5Represent arbitrary by R
1The group or the formula-OR of expression
4Group; And R
3Represent C
1-C
6Alkyl; Aryl; Heterocyclic group with 3 to 7 annular atomses, at least one is sulphur or nitrogen-atoms in described annular atoms; The perhaps group of formula (IV):
Wherein Y represents C
1-C
18Alkylidene group, phenylene, cyclohexylidene or biphenyl two bases.
12. method according to claim 11, wherein said acylphosphine oxide are the compounds of formula V:
Wherein:
R
1Represent C
1-C
12Alkyl, cyclohexyl or aryl; With
R
3Such as in claim 11 definition.
13. method according to claim 12, wherein each R
3Be independently selected from phenyl and have 1 to 4 halogenic substituent and/or C
1-C
6Alkyl substituent and/or C
1-C
6The phenyl of alkoxy substituent.
14. according to claim 12 or the described method of claim 13, wherein R
1Represent C
1-C
12Alkyl or phenyl, described phenyl are unsubstituted or have 1 to 3 C
1-C
6Alkyl or alkoxy substituent.
15. method according to claim 11, wherein said acylphosphine oxide are the compounds of formula (VI):
Wherein:
R
1And R
3Such as claim 11 definition; With
R
2aRepresent C
1-C
12Alkyl; C
3-C
7Cycloalkyl; Aryl; Aralkyl; Heterocyclic radical with 3 to 7 annular atomses, in these annular atomses, at least one is sulphur or nitrogen-atoms; Perhaps formula-OR
4Group, R wherein
4Such as claim 11 definition.
16. method according to claim 11, wherein said acylphosphine oxide are the compounds of formula (VII):
Wherein:
N is 0 or 1;
R
6Represent C
1-C
12Alkyl, C
1-C
6Alkoxyl group, phenyl or have 1 to 4 substituent phenyl, described substituting group is selected from C
1-C
6Alkyl, C
1-C
6Alkoxyl group and halogen atom; With
R
7, R
8, R
9, R
10, R
11And R
12Be identical or different each other, and each represent hydrogen atom, C
1-C
6Alkyl, C
1-C
6Alkoxyl group or halogen atom.
17. method according to claim 11; wherein said acylphosphine oxide is 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4; the 6-trimethylbenzoyl) phenyl phosphine oxide, ethyl 2; 4,6-trimethylbenzoyl diphenylphosphine acid esters or two (2,6-dimethoxy benzoyl)-2; 4,4-tri-methyl-amyl phosphine oxide.
18. according to each described method in the claim 9 to 17, wherein said stock is a paper.
19. according to each described method in the claim 9 to 18, wherein said file is a secure file.
20. method according to claim 19, wherein said secure file is a banknote.
21. as the purposes of photoinitiator, with the preparation gravure printing ink, described gravure printing ink does not show fluorescence in the visible wavelength district to the acylphosphine oxide of formula (I) when being exposed to UV-light in energy-curable intaglio printing inks:
Wherein:
R
1And R
2Be independently selected from C
1-C
12Alkyl; C
3-C
7Cycloalkyl; Aryl; Aralkyl; Heterocyclic group with 3 to 7 annular atomses, at least one is sulphur or nitrogen-atoms in described annular atoms; And has formula-COR
3Group; Perhaps R
2Representative has formula-OR
4Group, R wherein
4Represent C
1-C
6Alkyl, aryl, aralkyl or cation group or atom, perhaps R
2The group of representative formula (II):
Wherein X represents C
1-C
18Alkylidene group or biphenyl two bases, and R
5Represent arbitrary by R
1The group or the formula-OR of expression
4Group; And R
3Represent C
1-C
6Alkyl; Aryl; Heterocyclic group with 3 to 7 annular atomses, at least one is sulphur or nitrogen-atoms in described annular atoms; The perhaps group of formula (IV):
Wherein Y represents C
1-C
18Alkylidene group, phenylene, cyclohexylidene or biphenyl two bases.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0407473.8 | 2004-04-01 | ||
| GB0407473A GB2412660A (en) | 2004-04-01 | 2004-04-01 | Energy-curable intaglio printing inks |
| GB0420968.0 | 2004-09-21 | ||
| GB0502057.3 | 2005-02-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1961051A true CN1961051A (en) | 2007-05-09 |
Family
ID=32247721
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800179171A Pending CN1961052A (en) | 2004-04-01 | 2005-03-30 | Energy-curable intaglio printing inks |
| CNA2005800179167A Pending CN1961051A (en) | 2004-04-01 | 2005-03-30 | Photoinitiators for use in intaglio printing inks |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800179171A Pending CN1961052A (en) | 2004-04-01 | 2005-03-30 | Energy-curable intaglio printing inks |
Country Status (3)
| Country | Link |
|---|---|
| CN (2) | CN1961052A (en) |
| GB (1) | GB2412660A (en) |
| ZA (2) | ZA200608535B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592298A (en) * | 2014-12-31 | 2015-05-06 | 湖北固润科技股份有限公司 | Acylphosphine efficient photoinitiator and preparation method thereof |
| CN104995266A (en) * | 2013-02-21 | 2015-10-21 | 富士胶片株式会社 | Ink composition, inkjet recording method, printed matter, and high-molecular-weight polymerization initiator |
| CN110105470A (en) * | 2019-04-30 | 2019-08-09 | 同济大学 | Free Radical-Cationic Hybrid Photoinitiators and its preparation method and application |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8636307B2 (en) * | 2007-07-20 | 2014-01-28 | Sicpa Holding Sa | Intaglio printing inks |
| CN101874085B (en) * | 2007-09-25 | 2014-04-16 | 孟山都技术公司 | Use of oils with high concentrations of polyunsaturated fatty acids in plastics and surface coatings |
| CN103045011B (en) * | 2013-01-17 | 2014-03-19 | 佛山科学技术学院 | Blue ceramic ink-jet printing ink composition and preparation method thereof |
| CN111117339A (en) * | 2015-05-26 | 2020-05-08 | 苏州市贝特利高分子材料股份有限公司 | Preparation method of UV gravure ink for aramid paper |
| CN106638024A (en) * | 2016-12-15 | 2017-05-10 | 苏州吉谷新材料有限公司 | Heat sublimation printing ink |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH585624A5 (en) * | 1973-12-21 | 1977-03-15 | Sicpa Holding Sa | |
| GB1469717A (en) * | 1974-06-13 | 1977-04-06 | Thailand Bank Of | Printing inks |
| ES2077664T3 (en) * | 1989-12-07 | 1995-12-01 | Sicpa Holding Sa | HIGHLY REACTIVE PRINTING INKS. |
| AUPQ417399A0 (en) * | 1999-11-22 | 1999-12-16 | Note Printing Australia Limited | Intaglio printing inks |
-
2004
- 2004-04-01 GB GB0407473A patent/GB2412660A/en not_active Withdrawn
-
2005
- 2005-03-30 CN CNA2005800179171A patent/CN1961052A/en active Pending
- 2005-03-30 CN CNA2005800179167A patent/CN1961051A/en active Pending
-
2006
- 2006-10-12 ZA ZA200608535A patent/ZA200608535B/en unknown
- 2006-10-12 ZA ZA200608531A patent/ZA200608531B/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104995266A (en) * | 2013-02-21 | 2015-10-21 | 富士胶片株式会社 | Ink composition, inkjet recording method, printed matter, and high-molecular-weight polymerization initiator |
| US9902865B2 (en) | 2013-02-21 | 2018-02-27 | Fujifilm Corporation | Ink composition, inkjet recording method, printed matter, and high-molecular-weight polymerization initiator |
| CN104592298A (en) * | 2014-12-31 | 2015-05-06 | 湖北固润科技股份有限公司 | Acylphosphine efficient photoinitiator and preparation method thereof |
| CN110105470A (en) * | 2019-04-30 | 2019-08-09 | 同济大学 | Free Radical-Cationic Hybrid Photoinitiators and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2412660A (en) | 2005-10-05 |
| CN1961052A (en) | 2007-05-09 |
| ZA200608535B (en) | 2008-02-27 |
| GB0407473D0 (en) | 2004-05-05 |
| ZA200608531B (en) | 2008-06-25 |
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