CN110305527A - A kind of radiation curing gravure ink composition - Google Patents
A kind of radiation curing gravure ink composition Download PDFInfo
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- CN110305527A CN110305527A CN201810227986.4A CN201810227986A CN110305527A CN 110305527 A CN110305527 A CN 110305527A CN 201810227986 A CN201810227986 A CN 201810227986A CN 110305527 A CN110305527 A CN 110305527A
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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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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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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Abstract
A kind of radiation curing gravure ink composition includes: cationically polymerizable compound, oxygen heterocycle butane and cycloaliphatic epoxy comprising hydroxyl；Free-radical polymerised compound is selected from (methyl) acrylic ester monomer compound；Cationic photoinitiator；Radical photoinitiator；Pigment and filler.The printing ink composition does not use any volatile organic solvent, viscosity is low, good fluidity, printability and metastatic are good on the printer, and curing rate is fast, it can be realized high speed printing, coating attachment fastness suitable for a variety of substrates, and after solidifying is good, and wear-resisting property is excellent, printing appearance is good, odorlessness.
Description
Technical field
The invention belongs to radiation curing technology fields, and in particular to a kind of radiation curing gravure ink composition and its answer
With.
Background technique
With the continuous improvement of people's living standards, environmental protection, energy conservation have become the overall development of current printing packaging industry
Trend.Gravure printing ink is required to meet nontoxic, harmless, non-ignitable not quick-fried, low as an important technology branch therein
The performance indicators such as VOC emission, country have also put into effect corresponding professional standard " environmental labelling product technical requirements gravure ink and soft
Printing ink ".Under these circumstances, water-based ink is developed to be used to substitute solvent-based ink, however aquosity intaglio printing ink exists
Self-defect most highlightedly shows that energy consumption is high, production efficiency is low, ink attachment fastness is poor, is easy to appear anti-bonding when printing
Migration etc..
In recent years, occurs the report about UV curing intaglio printing ink successively.For example, application No. is 200910058357.4
Chinese patent application discloses a kind of gravure ink of radically curing, but it has dry incomplete, the printing solidification of thick ink film
Lines shrink serious defect afterwards.Application No. is 201310654113.2 Chinese patent applications to disclose a kind of aqueous UV gravure
Ink, but the ethyl alcohol containing 15-20% in formula, VOC emission are obvious.Application No. is the Chinese patent Shens of 201510993972.X
A kind of gravure ink of cationic curing please be disclose, compared with above-mentioned Free Radical Curable Ink, this ink adhesion is good, resistance to
Mill property is excellent, but there are curing rates it is slow, prepolymer and reactive diluent type are few, on the high side the problems such as.In addition, application
Number a kind of the recessed of free radical-cation-oxidation filming triple curable is disclosed for 201510267026.7 Chinese patent application
Printing ink, the ink main advantage are without volatile solvent, shorten and reprint the period, be not easy by set-off, but in its component
Free-radical polymerised compound accounts for 80% or more, and there are still the defects that lines after solidification are shunk, and curing rate only has 50m/
Min, it is difficult to reach the market application demand of linear velocity 200m/min or more, production efficiency is low.
Currently, market is low to viscosity, curing rate is fast, without volatile solvent and product attachment and wear-resisting property all very
Excellent new type radiation solidified gravure ink composition has very big demand.
Summary of the invention
In view of the deficiencies of the prior art with field growth requirement, it is molten without volatility that the purpose of the present invention is to provide one kind
Agent, low viscosity, curing rate is fast, solidify after the excellent radiation curing gravure ink composition of properties of coating.The composition
Curing system is mixed using cation-free radical, by selecting suitable pre- polycondensation monomer, radically curing speed can be given full play to
Fastly, cationic curing does not have the characteristics of oxygen inhibition, the physical property after effectively increasing rate of drying and drying, and gas after solidification
Taste is low, and printed matter appearance is good.
Specifically, radiation curing gravure ink composition of the invention, includes following component:
(A) cationically polymerizable compound, the oxygen heterocycle butane comprising hydroxyl and alicyclic epoxy close
Object；
(B) free-radical polymerised compound is selected from (methyl) acrylic ester monomer compound；
(C) cationic photoinitiator；
(D) radical photoinitiator；
(E) pigment；
(F) filler.
Each component will be described in more details below.
<(A) cationically polymerizable compound>
As component (A) cationically polymerizable compound, the oxygen heterocycle butane and ester ring type epoxy of hydroxyl
Compound is necessary component, and being applied in combination for the two brings required reactivity and application performance for gravure ink.
Described " oxygen heterocycle butane of hydroxyl " has normally understood in organic chemistry filed herein
Meaning, the i.e. compound containing at least one hydroxyl He at least one oxetane groups.
There is no particularly severe restriction to the specific category of the oxygen heterocycle butane of hydroxyl, but for recessed
The considerations of properties such as attachment fastness, curing rate, the viscosity of printing ink, preferably being selected from least one end-capping group is oxetanes
The substitution of group and hydroxyl or unsubstituted alkane and alkene, the H on oxetanes end group is optionally by C1-C4's
Replaced alkyl.
It is highly preferred that the oxygen heterocycle butane of the hydroxyl is that have at least one end-capping groupAlkane or alkene (therein * indicate connection site), optionally ,-the CH in non-terminated group2It can
Each independently by-O- ,-COO- ,-OCO- ,-SO2, 1,4- phenylene orIt is replaced, condition be two O not
It is connected directly.
Illustratively, the oxygen heterocycle butane of hydroxyl is preferably from the compound having the following structure:
Described " cycloaliphatic epoxy " refers to the compound with ester ring oxygroup herein.From further mentioning
From the aspect of high curing rate, it is contemplated that use the multifunctional ester ring in molecule with 2 or more ester ring oxygroups
Ester ring type in oxygen compound or molecule with 1 ester ring oxygroup and with unsaturated double-bonds groups such as vinyl
Epoxide.
As the cycloaliphatic epoxy being applicable in gravure ink of the present invention, preferably with the epoxy of epoxycyclohexyl
Compound, such as 3,4- epoxycyclohexyl-methyl -3 ', 4 '-epoxycyclohexylcarboxylates, modified -3, the 4- epoxy hexamethylene of 6-caprolactone
Ylmethyl -3 ', 4 '-epoxycyclohexylcarboxylates, bis- ((3,4- epoxycyclohexyl) methyl) adipate esters, 7-oxa-bicyclo[4.1.0,2-
(3,4- 7-oxa-bicyclo[4.1.0) ethyl trimethoxy silane, 3,4- epoxycyclohexyl-methyl methacrylate, 3,4- epoxy hexamethylene
Methyl acrylate, 1,2- epoxy -4- vinyl cyclohexane, 3,4- epoxycyclohexane carboxylate, 3,4- epoxycyclohexyl first
The polymerizate of base 3,4- epoxycyclohexyl formic acid esters and caprolactone, 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid
The polymerizate of ester and caprolactone, 4- methyl-1,2- 7-oxa-bicyclo[4.1.0,2,2- bis- (3,3 '-epoxycyclohexyl) propane, 2- (3,
4- 7-oxa-bicyclo[4.1.0) ethyl trimethoxy silane.
In component (A) cationically polymerizable compound, the oxygen heterocycle butane and ester ring type epoxy of hydroxyl
The mass ratio of compound is 2-5:1, preferably 2-4:1.
Other than the oxygen heterocycle butane of above-mentioned hydroxyl and cycloaliphatic epoxy, optionally, component
(A) also contain the cationically polymerizable compound of other classifications, including (but not limited to this) in: having different from above two
The oxygen heterocycle butane and epoxide and vinyl ethers compound of necessary component structure.Do not influencing this
Under the premise of goal of the invention, by using the cationically polymerizable compound of these other classifications in right amount, gravure oil can be optimized
The cost of ink, the overall applicability performance for a step control gravure ink of going forward side by side.Their total content (quality percentages in component (A)
Than) no more than 40%, preferably more than 20%, more preferably no more than 10%.
As the oxygen heterocycle butane of other classifications, monofunctional compound can be, be also possible to multiple functionalized
Close object.Simple function example includes (but not limited to this): 3- methyl -3- hydroxymethyl oxetane, 3- ethyl -3- hydroxymethyl
Oxetanes, 3- ethyl -3- (hexoxymethyl) oxetanes, 3- ethyl -3- (2- Ethylhexoxymethyl) oxa- ring
Butane, 3- ethyl -3- [(phenoxy group) methyl] oxetanes, 3- ethyl -3- (chloromethyl) oxetanes, isobutoxy first
Base (3- ethyl -3- oxetanylmethyl) ether, isobornyl oxygroup ethyl (3- ethyl -3- oxetanylmethyl)
Ether, isobornyl (3- ethyl -3- oxetanylmethyl) ether, 2- ethylhexyl (3- ethyl -3- oxetanyl first
Base) ether, ethyl diethylene glycol (DEG) (3- ethyl -3- oxetanylmethyl) ether etc..Multifunctional example includes (but not limited to this): double
[1- ethyl (3- oxetanyl)] methyl ether, bis- (chloromethyl) oxetanes of 3,3-, 3,7- bis- (3- oxetanyls)-
Bis- [(3- ethyl -3- oxetanylmethoxy) methyl] ethane of 5- oxa--nonane, 1,2-, the bis- [(3- ethyl -3- oxygen of 1,3-
Azetidine ylmethoxy) methyl] propane, ethylene glycol bis- (3- ethyl -3- oxetanylmethyl) ethers, tristane diyl
Dimethylene (3- ethyl -3- oxetanylmethyl) ether, trimethylolpropane tris (3- ethyl -3- oxetanyl first
Base) ether, 1,4- bis- [(3- ethyl -3- oxetanylmethoxy methoxyl group) methyl] benzene, the bis- (3- ethyl -3- oxetanyls of 1,4-
Methoxyl group) butane, bis- (3- ethyl -3- oxetanylmethoxy) hexanes of the 1,6-, (3- ethyl -3- oxa- of pentaerythrite three
Cyclobutane ylmethyl) ether, pentaerythrite four (3- ethyl -3- oxetanylmethyl) ether, the bis- (3- ethyl -3- of polyethylene glycol
Oxetanylmethyl) ether, dipentaerythritol six (3- ethyl -3- oxetanylmethyl) ether, five (3- of dipentaerythritol
Ethyl -3- oxetanylmethyl) ether, dipentaerythritol four (3- ethyl -3- oxetanylmethyl) ether etc..In addition,
Application No. is 201610548580.7,201610550205.6,201710706339.7 and 201710622973.2 China specially
Those oxygen heterocycle butanes disclosed in benefit application (herein introducing its full text using as reference) can also be used for combining
In object.
As the epoxide of other classifications, hydrogenated epoxy compound, aromatic epoxy compound and/or rouge can be
Fat race epoxide.
As above-mentioned hydrogenated epoxy compound, it is however preferred to have be directly or indirectly bonded in representative examples of saturated aliphatic ring-type hydrocarbon skeleton
On glycidyl ether compound, polyfunctional glycidyl ether's compound is suitable.Such hydrogenated epoxy compound
The preferably complete or partial hydride of aromatic epoxy compound, the more preferably hydrogenation of aromatic glycidyl ether compound
Object, the further preferably hydride of aromatic series polyfunctional glycidyl ether compound.Specifically, it can be selected from hydrogenated bisphenol A type
Epoxide, A Hydrogenated Bisphenol A S type ring oxygen compound, A Hydrogenated Bisphenol A F type ring oxygen compound etc..
Above-mentioned aromatic epoxy compound is compound in the molecule with aromatic rings and epoxy group.As aromatic ring
Oxygen compound can be the epoxy compound with the aromatic rings conjugated system such as bisphenol backbone, fluorene skeleton, biphenyl backbone, naphthalene nucleus, anthracene nucleus
Object etc..Wherein, in order to realize higher refractive index, the preferably compound with bisphenol backbone and/or fluorene skeleton, more preferably have
Thus the compound of fluorene skeleton can improve refractive index more significantly, and also can further improve release property.Additionally, it is preferred that
Epoxy group in aromatic epoxy compound is the compound of glycidyl, and the more preferable epoxy group is glycidyl ether
Compound (that is, aromatic glycidyl ether compound).In addition, the bromide using aromatic epoxy compound can also be realized more
High refractive index, thus be suitable, but since Abbe number can be improved slightly, thus preferably take the circumstances into consideration to use depending on the application.
As above-mentioned aromatic epoxy compound, preferred example includes bisphenol A type epoxy compound, bisphenol F type epoxy
Compound, fluorenes system epoxide, aromatic epoxy compound with bromine substituent etc..
As above-mentioned aromatic glycidyl ether compound, Epi-bis type diglycidyl ether type epoxy resin, height can be
Molecular weight Epi-bis type diglycidyl ether type epoxy resin, novolaks, aralkyl-type diglycidyl ether type epoxy resin etc..
Epi-bis type diglycidyl ether type epoxy resin can be through bis-phenols such as bisphenol-A, Bisphenol F, bisphenol S, fluorenes bis-phenols
Resin obtained from the condensation reaction of class and epoxyhalopropane.
High molecular weight Epi-bis type diglycidyl ether type epoxy resin, can be by above-mentioned Epi-bis type glycidol ether
Type epoxy resin further occurs to set obtained from addition reaction with bisphenols such as above-mentioned bisphenol-A, Bisphenol F, bisphenol S, fluorenes bis-phenols
Rouge.
As above-mentioned aromatic glycidyl ether compound, preferred example includes (but not limited to this): by Japanese epoxy
The bisphenol A-types compounds such as 828EL, 1003,1007 of the production of resin society, are produced by OSAKAGAS CHEMICALS
Fluorenes based compound such as ONCOATEX-1020, ONCOATEX-1010, OGSOLEG-210, OGSOLPG etc..
Above-mentioned aliphatic epoxy compound is the compound with aliphatic epoxy base, such as aliphatic glycidyl ether type ring
Oxygen resin.The preferred embodiment of aliphatic glycidyl ether type epoxy resin include (but not limited to this) by polyol with
Resin obtained from the condensation reaction of epoxyhalopropane, the polyol can be selected from ethylene glycol, diethylene glycol (DEG), triethylene glycol,
Tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, four propylene glycol, polypropylene glycol, glycerol, diglycerol, four
Glycerol, polyglycereol, trimethylolpropane and its polymer, pentaerythrite and its polymer, mono-/multi- carbohydrate (such as glucose, fruit
Sugar, lactose, maltose etc.), etc..Wherein, there is propylene glycol skeleton, alkylene backbone, oxyalkylene skeleton in center framework
Aliphatic glycidyl ether type epoxy resin be more particularly suitable.
The example of above-mentioned vinyl ethers compound includes (but not limited to this): the aryl vinyls such as Vinyl phenyl ether
Ether；The alkyl vinyl ethers such as n-butyl vinyl ether, n-octyl vinyl ethers；The cycloalkyl vinyls base such as cyclohexyl vinyl ether
Ether；The hydroxyls vinyl ethers such as 2- hydroxyethyl vinylethers, diethylene glycol monovinyl base ether, 2- hydroxy butyl vinyl ether；Quinhydrones
Divinyl ether, 1,4- butanediol divinyl ether, hexamethylene divinyl ether, cyclohexanedimethanol divinyl base ether, second two
Polyfunctional vinyls ether such as alcohol divinyl ether, diethylene glycol divinyl ether, triethyleneglycol divinylether etc..
Than that described above, the cationically polymerizable compound of other classifications also can be used has difference in the molecule
The compound of the cationic polymerizable group of type.For example, as having epoxy group (such as alicyclic epoxy simultaneously in the molecule
Base) and vinyl ether group example, can be used Japanese Unexamined Patent Publication 2009-242242 bulletin in record those of compound；As
There is the example of oxetanyl and vinyl ether group simultaneously in the molecule, Japanese Unexamined Patent Publication 2008-266308 public affairs can be used
Those of record compound in report.
Content of component (A) the cationically polymerizable compound in gravure ink composition can be according to substrate type and performance
It needs to be adjusted in right amount.Expediently, mass ratio of the component (A) in radiation curing gravure ink composition of the invention is
30-80%, preferably 40-70%.
<(B) free-radical polymerised compound>
The free-radical polymerised compound of frequent species is easy to know for the technical staff in radiation curing field.
In gravure ink composition of the invention, the free-radical polymerised compound as component (B) is selected from (methyl) acrylate
Class monomeric compound.
As example, (but not limited to this) can be enumerated: (methyl) methyl acrylate, (methyl) ethyl acrylate, (first
Base) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) isoamyl acrylate, (first
Base) cyclohexyl acrylate, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid-2-ethyl caproite, (methyl) Isodecyl
Ester, (methyl) acrylic acid n-dodecane base ester, the different tetradecane base ester of (methyl) acrylic acid, (methyl) acrylic acid n-octadecane base
Ester, (methyl) acrylic acid n-butoxy ethyl ester, butoxy diethylene glycol (methyl) acrylate, methoxy triethylene (methyl)
Acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) benzyl acrylate,
(methyl) phenoxyethyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) propylene
Sour 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylate, (methyl) acrylic acid two
Ethylamino ethyl ester, 2- methacryloxyethyl -2- hydroxypropyl phthalic acid ester, (methyl) glycidyl
Ester, 2- methyl -2- acrylic acid -2- (phosphono oxygroup) ethyl ester, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl)
Acrylate, triethylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, 1,4- butanediol two (methyl)
Acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, two (first of 1,9- nonanediol
Base) acrylate, 1,10- decanediol two (methyl) acrylate, trimethylolpropane trimethacrylate, glycerol two (methyl) third
Olefin(e) acid ester, 2- hydroxyl 3- acryloxypropyl (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate,
(methyl) acrylic acid trifluoro ethyl ester, (methyl) perfluoroethyl octyl ethyl ester, γ-(methyl) acryloxypropyl trimethoxy
Silane, isocyanic acid 2- (methyl) acryloyloxyethyl ester, bis- (acryloxy) ethyl esters of isocyanic acid 1,1-, isocyanic acid 2- (2- first
Base acryloyloxyethoxy) ethyl ester etc..
Mass ratio of the component (B) in radiation curing gravure ink composition of the invention is 10-50%, preferably 15-
30%.
<(C) cationic photoinitiator>
After determining component (A) cationically polymerizable compound, select applicable cationic photoinitiator to ability
It is relatively easy to for field technique personnel.In general, can attempt using existing oxetanes class and/or epoxies sun from
Has photoinitiator those of in sub-light curing system.
In gravure ink composition of the invention, it is preferable that component (C) cationic photoinitiator can be selected from salt compounded of iodine,
The combination of one or more of sulfosalt, aryl cyclopentadienyl molysite.
Based on the considerations of the composite factors such as cost, for example light-initiated efficiency of the effect being used cooperatively, curing rate, component (C)
It is preferred that salt compounded of iodine and/or sulfosalt photoinitiator, particularly preferably with the chemical combination of the structure as shown in following formula (I) and/or (II)
Object:
Wherein, R1And R2It is independently represented each other hydrogen, C1-C20Linear or branched alkyl group, C4-C20Cycloalkyl-alkyl or
Alkyl-cycloalkyl, and the acyclic-CH in these groups2Optionally replaced-O- ,-S- or 1,4- phenylene；
R3And R4It is independently represented each other hydrogen, C1-C20Linear or branched alkyl group, C4-C20Cycloalkyl-alkyl or alkyl ring
Alkyl, C6-C20Aryl substituted or unsubstituted, and the acyclic-CH in these groups2It is optionally sub- by-O- ,-S- or 1,4-
Replaced phenyl；
R5Represent C6-C20Aryl substituted or unsubstituted, C6-C20Alkylaryl substituted or unsubstituted, C1-C20Straight chain
Or branched alkyl, C4-C20Cycloalkyl-alkyl or alkyl-cycloalkyl, substitution or unsubstituted Phenylsulfanylphenyl, and these bases
Acyclic-CH in group2Optionally replaced carbonyl ,-O- ,-S- or 1,4- phenylene；
R6And R7It is independently represented each other alkyl, hydroxyl, alkoxy, alkyl-carbonyl, aryl carbonyl, alkoxy carbonyl, fragrant oxygen
Base carbonyl, arylthiocarbonyl, acyloxy, arylthio, aryl, heterocyclic hydrocarbyl, aryloxy group, alkyl sulphinyl, aryl sulfenyl
Base, alkyl sulphonyl, aryl sulfonyl, hydroxyl (poly-) alkylidene oxygroup, substitutive amino, cyano, nitro or halogen atom,
m1、m2Respectively indicate R6And R7Number, indicate the integer of 0-4.
X-It is independently represented each other M-、ClO4 -、CN-、HSO4 -、CF3COO-、(BM4)-、(SbM6)-、(AsM6)-、(PM6)-、Al
[OC(CF3)3]4 -, sulfonate ion, B (C6M5)4 -Or [(Rf)bPF6 - b]-, wherein M is F or Cl, and Rf indicates that >=80% hydrogen is former
The alkyl that son is replaced by fluorine atoms, b indicates 1~5 integer, and b Rf group is identical or different.
As preferred structure, in the compound of structure shown in formula (I) and (II):
R1And R2It is independently represented each other hydrogen, C1-C12Linear or branched alkyl group, C4-C10Cycloalkyl-alkyl or alkyl ring
Alkyl, and the acyclic-CH in these groups2Optionally replaced-O-；
R3And R4It is independently represented each other hydrogen, C1-C10Linear or branched alkyl group, C4-C10Cycloalkyl-alkyl or alkyl ring
Alkyl, C6-C12Aryl substituted or unsubstituted, and the acyclic-CH in these groups2It is optionally sub- by-O- ,-S- or 1,4-
Replaced phenyl；
R5Represent C6-C10Aryl substituted or unsubstituted, C6-C10Alkylaryl substituted or unsubstituted, substitution or not by
Substituted Phenylsulfanylphenyl, and the acyclic-CH in these groups2Optionally by carbonyl ,-O- ,-S- or 1,4- phenylene institute
Replace；
R6And R7Indicate C1-C10Linear or branched alkyl group, C1-C10Straight or branched alkoxyl, C1-C10Alkyl oxycarbonyl
Base and halogen.
It is further preferred that above-mentioned salt compounded of iodine and sulfosalt photoinitiator cationic portion can be enumerated such as flowering structure:
It is further preferred that above-mentioned salt compounded of iodine and sulfosalt photoinitiator anion part can enumerate: Cl-、Br-、
PF6 -、SbF6 -、AsF6 -、BF4 -、C4F9SO3 -、B(C6H5)4 -、C8F17SO3 -、CF3SO3 -、Al[OC(CF3)3]4 -、(CF3CF2)2PF4 -、
(CF3CF2)3PF3 -、[(CF3)2CF2]2PF4 -、[(CF3)2CF2]3PF3 -、[(CF3)2CFCF2]2PF4 -、(CF3)2CFCF2]3PF3 -。
In addition, the commercially available cationic photoinitiator of homogeneous structure can also be used for component of the invention (C), can enumerate
(but not limited to this): the product of trade name PAG20001, PAG20002, PAG30201, PAG30101 are (by Changzhou electronic strong
The production of new material limited liability company), by the Irgacure250 etc. of BASF Corp. of Germany's production.
By percentage to the quality, content of the component (C) in gravure ink composition of the invention is 1-20%, preferably
3-10%.
<(D) radical photoinitiator>
After determining component (B) free-radical polymerised compound, select applicable radical photoinitiator to ability
It is relatively easy to for field technique personnel.In general, it can attempt solid using existing (methyl) esters of acrylic acid free radical light
Those of in change system have photoinitiator, such as can be selected from benzoin class, acetophenones, Alpha-hydroxy ketone, alpha-amido ketone,
One of acyl group phosphorous oxides, benzophenone, thioxanthones, Anthraquinones, oxime ester lightlike initiating agent are a variety of.
Example include (but not limited to this): trade name Irgacure 651, Irgacure 184, Irgacure 907,
Irgacure 369、Irgacure 500、Irgacure 1000、Irgacure 819、Irgacure 1700、Irgacure
261, the production of Irgacure 784, Irgacure 1173, Irgacure 2959, Irgacure 4265, Irgacure 4263
Product (are produced) by BASF AG；Trade name SR1130, SR1137, SR1136, SR1135, SR1010, SR1011,
Product (being produced by Sartomer) of SR1012, SR1125 etc..
By percentage to the quality, content of the component (D) in gravure ink composition of the invention is 1-20%, preferably
3-10%.
<(E) pigment>
One or more pigment are generally comprised in gravure ink composition as colorant.Pigment can be inorganic pigment or
Organic pigment, and can be any color, including but not limited to black, blue, brown, cyan, green, white, purple, magenta,
The spot color of red, orange and yellow and their mixtures.
Applicable organic pigment can be perylene, phthalocyanine dye (such as phthalocyanine green, phthalocyanine blue), cyanine pigment (Cy3,
Cy5 and Cy7), naphthalene phthalocyanine color, nitroso pigments, azo pigments, diazo pigment, diazonium condensation pigment, basic dye pigments,
Alkali blue pigment, indigo pigment, root skin red pigment, Kui quinacridone pigment, isoindolenone pigments, dioxazines pigment, carbazole two
Oxazines purple dye, alizarine lake pigment, phthalic amide pigment, carmine lake pigment, tetrachloroisoindolinone pigment, purple
The mixture of cyclic ketones pigment, anthraquinone pigment and quinophthalone pigments etc. and both the above or more or more than derivative.
Applicable inorganic pigment includes, such as the oxidation of metal oxide (such as titanium dioxide, electric conductivity titanium dioxide), iron
Object (such as red iron oxide, yellow iron oxide, black iron oxide and transparent ferric oxide), aluminum oxide, Si oxide, carbon black face
Material, metal sulfide, metal chloride etc. and their mixture of two or more.
In gravure ink composition of the invention, by percentage to the quality, the content of component (E) is 2-20%, preferably
5-15%.
<(F) filler>
The type of component (F) filler is not particularly limited, those conventional use of types in gravure ink can be used.
Typically, filler can be selected from the mixture of one or both of nanometer calcium carbonate, silica.
By percentage to the quality, content of the component (F) in gravure ink composition is 0-20%, preferably 0-10%.
<other optional components>
Other than said components (A)-(F), according to products application environment needs, gravure ink composition of the invention may be used also
Selectively add organic and/or inorganic assistant commonly used in the art, including (but not limited to this) levelling agent, dispersing agent, solid
Agent, surfactant, defoaming agent, storage reinforcing agent etc., this is to be easy determination to those skilled in the art.With quality
Percentages, auxiliary agent total content are 0-5%, preferably 0-3%.
In addition, sensitizer can also be added in system for the purpose of promoting gravure ink sensitivity.Especially when radiating light source is
When LED, it is intended to add sensitizer in gravure ink composition.The type of sensitizer can be pyrazoline compounds, a word used for translation
Pyridine class compound, anthracene compound, coumarin kind compound, tertiary amine compounds etc..As anthracene class sensitiser compounds, especially
It is preferred that the compound with the structure as shown in following formula (III) and/or (IV):
In logical formula (III), R8Indicate C1-C12Alkyl, C1-C12Aryl, C1-C8Alkoxy or aryloxy group, C3-
C12Naphthenic base, C4-C12Alkyl-cycloalkyl or cycloalkyl-alkyl, wherein one or more hydrogen in these groups can be by halogen
Replaced element, hydroxyl；X1And Y1Hydrogen, alkyl, alkoxy, halogen atom, nitro, sulfonic group, hydroxyl, amido are indicated independently of one another.
In logical formula (IV), R9Indicate C1-C12Alkyl, C1-C12Aryl, C1-C8Alkoxy or aryloxy group C3-C12
Naphthenic base, C4-C12Alkyl-cycloalkyl or cycloalkyl-alkyl, wherein one or more hydrogen in these groups can by halogen,
Replaced hydroxyl；N1 and n2 indicates the integer of 0-4, X independently of one another2And Y2Can be same or different, it indicates independently of one another
When hydrogen, alkyl, alkoxy, halogen atom, nitro, sulfonic group, hydroxyl, amido, n1 and n2 indicate 2 or more, X2And Y2It can be mutually the same
Or it is different.
Illustratively, anthracene compound can be one of following shown compound or multiple combinations:
Mass percentage content of the sensitizer in gravure ink composition is 0-5%, preferably 0-2%.
Under the radiation of the energy such as ultraviolet light, visible light, infrared ray, electron beam, laser, gravure ink composition of the invention
Polymerization reaction occurs, to realize rapid draing.As the light source for assigning energy, preferably dominant wavelength is in the region of 250-450nm
Interior, example includes ultrahigh pressure mercury lamp, high-pressure sodium lamp, medium pressure mercury lamp, mercury xenon lamp, metal halide lamp, high-power metallic halide
Lamp, xenon lamp, pulsed illumination xenon lamp, deuterium lamp, LED light, fluorescent lamp, Nd-YAG3 times of wave laser, He-Cd laser, N_2 laser, Xe-Cl
The various light sources such as excimer laser, Xe-F excimer laser, semiconductor excitation Solid State Laser.
Radiation curing gravure ink composition of the invention is can be obtained into the mixing of each component ingredient, specific preparation process can
Referring to conventional method those of in radiation-curable composition field.Typically, preparation process includes: in constant temperature and humidity and to avoid spoke
It penetrates under conditions of light source, ingredient is pre-dispersed, and grinding, (strainer filtering through predetermined size obtains having required partial size for filtering
Product).
Radiation curing gravure ink composition of the invention does not use any volatile organic solvent, and viscosity is low, mobility
Good, printability and metastatic are good on the printer, can be realized high speed printing, and be suitable for a variety of substrates, especially paper,
The carriers such as plastics, film surface.The ink solidification speed is fast, and the coating attachment fastness after solidification is good, and wear-resisting property is excellent, print
Product appearance is good, odorlessness, has the very strong market competitiveness.
Specific embodiment
Below with reference to specific embodiment, invention is further described in detail, but should not be construed as to the present invention
The limitation of protection scope.
1, the preparation of radiation curing gravure ink composition
It is formulated according to shown in embodiment 1-10 in table 1, raw material is used into high-speed mixer at the uniform velocity in yellow fluorescent lamp laboratory
Then stirring 1 hour is ground using grinding machine, after by 1 μm of partial size strainer filtering, obtain radiation curing gravure ink
Composition.
Unless otherwise instructed, quantity described in each embodiment is parts by weight.
Table 1
In table 1, the concrete meaning of each component is as follows:
A1-1: compound 1；
A1-2: compound 2；
A1-3: compound 3；
A1-4: compound 4；
A1-5: compound 5；
A1-6: compound 6；
A1-7: compound 7；
A1-8: compound 8；
A1-9: compound 9；
A1-10: compound 10；
A2-1:3,4- epoxycyclohexyl-methyl -3 ', 4 '-epoxycyclohexyl formic acid esters, Jiangsu Tai Teer new material science and technology have
Limit company；
A2-2: bis- ((3,4- epoxycyclohexyl) methyl) adipate esters, Jiangsu Tai Teer new material Science and Technology Ltd.；
B-1: trimethylolpropane trimethacrylate, Sartomer；
B-2: tripropylene glycol diacrylate, Sartomer；
C-1: bis- (4- (diphenyl sulfonium) phenyl) bis- hexafluorophosphates of thioether-and 4- (thiophenyl) phenyl diphenyl sulphur hexafluoro
Phosphatic salt-mixture, Changzhou Tronly New Electronic Materials Co., Ltd.；
C-2:4,4'- xylyl iodine hexafluorophosphate, Changzhou Tronly New Electronic Materials Co., Ltd.；
C-3:
D-1:1- hydroxycyclohexyl phenyl ketone, BASF Corp. of Germany；
D-2:2- methyl-1-[4- (methyl thio) phenyl]-2- (4- morpholinyl)-1- acetone, BASF Corp. of Germany；
Red pigment: Irgalite 2BP, BASF；
Blue pigment: Heliogen K7090, BASF；
Yellow uitramarine: Paliotol K0961HD, BASF；
Black pigment: carbon black MA-11, Mitsubishi chemistry；
Filler: silica A-200, Germany win wound Degussa Specialty Chemical Co., Ltd；
Sensitizer -1:9,10- dibutyl anthracene ether；
Sensitizer -2:2- ethyl anthracene -9,10- diethylester；
Sensitizer -3:
Levelling agent: BYK 333, Germany win wound Degussa Specialty Chemical Co., Ltd；
Polymerization inhibitor: hindered nitroxyl stabilizers
2, ink performance test and evaluation
It is printed using the solvent-free intaglio press of loose moral (model: A380), it is 395nm's that wavelength is added on machine
LED light is as radiating light source.
Referring to QBT 1046-2012 intaglio plate plastic film table printing ink professional standard, the sample of embodiment 1-10 is carried out
Performance test and evaluation.
(1) ink viscosity is tested
For solvent-free gravure ink, viscosity height directly affects the transfer performance of ink to influence the outer of printing
It sees.By machine test discovery upper in the solvent-free intaglio press of loose moral (model: A380), ink viscosity is special in 10-20s
Suitably.
Referring to GB/T 13217.4-2008 gravure ink viscosity test standard, the ink viscosity of embodiment 1-10 is carried out
Test, unit s.
(2) ink setting velocity test
Ink to be measured is transferred in PET film by A380 intaglio press, about 10 μm of thickness.Use wavelength for
The LED light source of 395nm irradiates, intensity 15w/cm2.It is touched referring to paint film drying time testing standard GB/T 1728-1979 middle finger
Method evaluates surface cure situation, i.e., touches coating with finger, dry without fingerprint confirmation form face with surface slip, tack-free, pressing
It is dry.
Rate of drying indicates with reaching the maximum line velocity of dry tack free effect, unit m/min.
(3) the storage stability test of ink
Referring to GB-T 6753.3-1986 ink storage stability testing method, the storage stability of ink to be measured is carried out
Measurement.Specific method is: ink being placed in 50 DEG C of baking ovens, is measured after 7 days to the viscosity of ink.Opinion rating is as follows:
Zero: viscosity increases ratio below 5%；
◎: viscosity increases ratio and is greater than 5%, and less than 10%；
●: viscosity increases ratio and is greater than 10%.
Evaluation result is summarized in table 2.
Table 2
It can see from the test result of upper table, the gravure ink composition using the embodiment 1-10 of inventive formulation is viscous
Spend low, storage stability is good, and radiation curing speed reaches 270m/min or more, hence it is evident that be more than that the prior art is no more than 200m/
The curing rate of min, production efficiency greatly improve.
3, coating performance test and evaluation
Under the conditions of ensuring that dry most slow linear velocity (270m/min) can be fully cured in gravure ink, by embodiment 1-
10 gravure ink is printed on PET film substrate, and thickness is about 10 μm, after placing for 24 hours, to the physical property of solidify coating into
Row test and evaluation, including attachment fastness, wearability, printing appearance and smell residual.
(1) attachment fastness is tested
It is carried out according to GB/T 13217.7-91 base gravure ink examination criteria, the specific method is as follows: in 25 ± 1 DEG C, humidity
Under the conditions of 65% ± 5%, by the tape-stripping for complying with standard GB 7707 in ink printing surface, rolled back and forth on adhesive tape nip drum machine
Pressure 3 times.5min is placed, by specimen holder on A disk, the adhesive tape appeared is fixed on B disk, is then switched on, and A disk is with speed 0.6-
Adhesive tape is opened in 1.0m/s rotation, is covered on the translucent millimeter ruled paper of wide 20mm and is taken off part.It is counted shared by ink layer respectively
Lattice number and the ink layer that is broken away shared by lattice number, be calculated as follows:
A (%)=[A1/ (A1+A2)] × 100%
In formula, A indicates that ink attachment fastness, A1 indicate that the lattice number of ink layer, A2 indicate the lattice number for the ink layer being broken away.
A >=90 are understood to meet performance indicator.
(2) wearability test
It is measured according to " the measurement rotation rubber grinding wheel method of GB/T1768-2006 paint and varnish wearability ".Specifically
Implementation method is as follows:
Under 23 ± 2 DEG C, 50 ± 5% relative humidity, by 500g counterweight aggravate on elastic grinding wheel, then be fixed on grind
The elastic grinding wheel friction paint film on tester is consumed, paint film is indicated by the mass loss size of paint film after 500 rub cycles
Wearability, unit g/500r.
Wearing quality lower than 0.030g/500r is considered as the extraordinary product of performance.
(3) printing appearance is tested
It is tested according to GB/T 7707-2008 intaglio plate decoration printed matter standard, the specific method is as follows: printing is placed on
Under the sight sample light source of compound 3 defined of CY/T, identified by range estimation.Printing is clean and tidy, without obvious ink stain, hangover, residual
It lacking, knife silk, edge is bright and clean, and it is good colour, without obvious water wave shape, has no obvious deformation and incomplete, that is, be considered qualification.
(4) smell residue analysis
Product after solidification is immediately placed in hermetic bag, sealing is placed 24 hours at room temperature, is then opened sack and is used
Artificial Olfactory is judged.Opinion rating is as follows:
Zero: without obvious smell；
×: penetrating odor.
Evaluation result is summarized in table 3.
Table 3
It can be seen from the evaluation result of table 3 after gravure ink of the invention solidification, coating adhesion is good, wearability
Excellent, printing pattern is clean and tidy, and the smooth of the edge is good colour, and product is without obvious smell.
4, performance is further tested and is evaluated
Radiation curing gravure ink composition of the invention is respectively applied to paper and plastic basis material, is applied to performance
Make further verifying.
(1) paper substrate
Referring to the requirement in GB/T 26461-2011 paper gravure ink evaluation standard to substrate and test method, to this
The performance that invention radiation curing gravure ink composition is applied to paper substrate is evaluated.
By formula preparation printing ink composition in table 4, ink is printed by the solvent-free intaglio press of loose moral (model: A380)
Brush is on meeting 10335.1 printing rubber millboard of GB/T, print speed printing speed 270m/min, using high-pressure sodium lamp (RW-UV.70201)
Carry out radiation curing, radiation energy about 200mj/cm2, the printed patterns that thickness is about 10 μm are obtained, referring next to hereinbefore
Evaluation method is to attachment fastness, wearability, printing appearance and odor profiles evaluates.
Test result is compiled in table 4.
Table 4
(2) plastic film substrate
Referring to being wanted in GB/T 1046-2012 intaglio plate plastic film table printing ink evaluation criterion to substrate and test method
It asks, the performance for being applied to different types of plastic film substrate to radiation curing gravure ink composition of the present invention is commented respectively
Valence.
By formula preparation printing ink composition in table 5, ink is divided by the solvent-free intaglio press of loose moral (model: A380)
It is not printed on PET, PVC, PP and PE substrate, print speed printing speed 270m/min, is carried out using high-pressure sodium lamp (RW-UV.70201)
Radiation curing, radiation energy about 200mj/cm2, the printed patterns that thickness is about 10 μm are obtained, referring next to evaluation hereinbefore
Method is to attachment fastness, wearability, printing appearance and odor profiles evaluates.
Test result is compiled in table 5.
Table 5
In terms of from the test result of table 4 and table 5, radiation curing gravure ink composition of the invention can be suitable for different bases
Material surface, and all have excellent application performance.
Claims (14)
1. a kind of radiation curing gravure ink composition includes following component:
(A) cationically polymerizable compound, oxygen heterocycle butane and cycloaliphatic epoxy comprising hydroxyl；
(B) free-radical polymerised compound is selected from (methyl) acrylic ester monomer compound；
(C) cationic photoinitiator；
(D) radical photoinitiator；
(E) pigment；
(F) filler.
2. radiation curing gravure ink composition according to claim 1, it is characterised in that: the oxa- ring of the hydroxyl
Butane compounds are selected from the substitution or unsubstituted alkane that at least one end-capping group is oxetane groups and hydroxyl
Hydrocarbon and alkene, the H on oxetanes end group is optionally by C1-C4Alkyl replaced.
3. radiation curing gravure ink composition according to claim 1 or 2, it is characterised in that: the oxygen of the hydroxyl
Azetidine class compound is that have at least one end-capping groupAlkane or alkene, optionally, non-envelope
- CH in end group group2It can be each independently by-O- ,-COO- ,-OCO- ,-SO2, 1,4- phenylene orIt is taken
Generation, condition are that two O are not connected directly.
4. radiation curing gravure ink composition according to claim 1, it is characterised in that: the alicyclic epoxy closes
Object is the epoxide with epoxycyclohexyl.
5. radiation curing gravure ink composition according to claim 1, it is characterised in that: the oxetanes of hydroxyl
The mass ratio of class compound and cycloaliphatic epoxy is 2-5:1, preferably 2-4:1.
6. radiation curing gravure ink composition according to claim 1, it is characterised in that: component (A) is in radiation curing
Mass ratio in gravure ink composition is 30-80%, preferably 40-70%.
7. radiation curing gravure ink composition according to claim 1, it is characterised in that: component (B) is in radiation curing
Mass ratio in gravure ink composition is 10-50%, preferably 15-30%.
8. radiation curing gravure ink composition according to claim 1, it is characterised in that: component (C) cationic light
Initiator is selected from the combination of one or more of salt compounded of iodine, sulfosalt, aryl cyclopentadienyl molysite.
9. radiation curing gravure ink composition according to claim 1 or 8, it is characterised in that: by percentage to the quality,
Content of the component (C) in gravure ink composition is 1-20%, preferably 3-10%.
10. radiation curing gravure ink composition according to claim 1, it is characterised in that: by percentage to the quality, group
Dividing the content of (D) in gravure ink composition is 1-20%, preferably 3-10%.
11. radiation curing gravure ink composition according to claim 1, it is characterised in that: component (F) filler is selected from and receives
The mixture of one or both of rice calcium carbonate, silica.
12. radiation curing gravure ink composition according to claim 1, it is characterised in that: also contain sensitizer.
13. radiation curing gravure ink composition according to claim 1, it is characterised in that: the dominant wavelength of radiating light source
In the regional scope of 250-450nm.
14. application of the radiation curing gravure ink composition of any of claims 1-13 in intaglio printing.
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| CN201810227986.4A CN110305527A (en) | 2018-03-20 | 2018-03-20 | A kind of radiation curing gravure ink composition |
| US16/982,076 US11787959B2 (en) | 2018-03-20 | 2019-03-20 | Radiation curable gravure ink |
| PCT/CN2019/078860 WO2019179460A1 (en) | 2018-03-20 | 2019-03-20 | Radiation-curable gravure ink |
| JP2020548977A JP7114725B2 (en) | 2018-03-20 | 2019-03-20 | Radiation-curable gravure printing ink |
| EP19772222.6A EP3770221A4 (en) | 2018-03-20 | 2019-03-20 | Radiation-curable gravure ink |
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Cited By (3)
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| CN112062675A (en) * | 2020-09-15 | 2020-12-11 | 常州速固得感光新材料有限公司 | Monomer with free radical and cation dual curing functions, preparation method and radiation curing gravure ink |
| CN112898817A (en) * | 2021-03-25 | 2021-06-04 | 中钞油墨有限公司 | LED-UV curing offset printing ink |
| CN112980239A (en) * | 2021-03-25 | 2021-06-18 | 中钞油墨有限公司 | LED-UV (light-emitting diode-ultraviolet) curing embossing printing ink |
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| CN1344302A (en) * | 1998-12-11 | 2002-04-10 | 太阳化学公司 | Radiation curable water based cationic inks and coatings |
| CN107001838A (en) * | 2014-12-11 | 2017-08-01 | 株式会社Lg化学 | Photosensitive colored ink composition for frame, the frame pattern using its formation and the display panel including the frame pattern |
| CN107300831A (en) * | 2016-04-15 | 2017-10-27 | 常州强力电子新材料股份有限公司 | A kind of curable compositions solidified applied to LED light |
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| CN1344302A (en) * | 1998-12-11 | 2002-04-10 | 太阳化学公司 | Radiation curable water based cationic inks and coatings |
| CN107001838A (en) * | 2014-12-11 | 2017-08-01 | 株式会社Lg化学 | Photosensitive colored ink composition for frame, the frame pattern using its formation and the display panel including the frame pattern |
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| CN112062675A (en) * | 2020-09-15 | 2020-12-11 | 常州速固得感光新材料有限公司 | Monomer with free radical and cation dual curing functions, preparation method and radiation curing gravure ink |
| CN112898817A (en) * | 2021-03-25 | 2021-06-04 | 中钞油墨有限公司 | LED-UV curing offset printing ink |
| CN112980239A (en) * | 2021-03-25 | 2021-06-18 | 中钞油墨有限公司 | LED-UV (light-emitting diode-ultraviolet) curing embossing printing ink |
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