CN110305526A

CN110305526A - A kind of radiation curing gravure ink composition containing modified pigment

Info

Publication number: CN110305526A
Application number: CN201810227962.9A
Authority: CN
Inventors: 钱彬; 杨金梁; 严春霞
Original assignee: Changzhou Green Photosensitive New Material Co Ltd
Current assignee: Changzhou Green Photosensitive New Material Co Ltd
Priority date: 2018-03-20
Filing date: 2018-03-20
Publication date: 2019-10-08

Abstract

The present invention discloses a kind of radiation curing gravure ink composition containing modified pigment, includes modified pigment, cationically polymerizable compound, free-radical polymerised compound, cationic photoinitiator and radical photoinitiator.The modified pigment includes pigment and the inorganic oxide nanoparticles for being coated on surface of pigments, and DBP oil absorption is 150-250ml/100g, and partial size is 0.01-1 μm, pH value 4.5-10.The printing ink composition is free of any volatile organic solvent, and viscosity is low, and storage stability is good, has excellent curing rate, and the printing appearance after solidifying is good, and adhesive force and wearability are excellent, odorlessness.

Description

A kind of radiation curing gravure ink composition containing modified pigment

Technical field

The invention belongs to radiation curing and technical field of ink, and in particular to a kind of radiation curing containing modified pigment is recessed Stamp-pad ink ink composition.

Background technique

Gravure ink is also gravure liquid ink, is a kind of coloured colloidal dispersion system, can use printing side appropriate Formula is coated on substrate, makes it that character pattern and various colors be presented.

Gravure ink is Volatile solvent type ink mostly, by pigment, hard resin, volatile solvent, filler and addition Agent composition.With the reinforcement of people's environmental protection and awareness of saving energy, water-based ink, light consolidate ink, electron beam ink etc. with respect to " green " Ink has gradually developed, and gradually replaces solvent ink and be applied.Such as application No. is 200580017917.1, 201510267026.7,201510994588.1 Chinese patent application, the United States Patent (USP) of Publication No. US2009/0136759A Application, discloses the energy-curable gravure ink without volatile solvent.However, the focus of these prior arts is most Concentrate on whether engraving plate cylinder curing ink is easy to wiping, printing appearance, attachment fastness, wearability, weatherability etc., to such as What improves ink storage stability, improves that production efficiency is rare is related to, and also lacks effective solution.

Summary of the invention

In view of the deficiencies of the prior art with technology growth requirement, the purpose of the present invention, which essentially consists in, provides one kind containing modification The radiation curing gravure ink composition of pigment.The printing ink composition mixes curing system using cation-free radical, and contains Specific modified pigment is free of any volatile organic solvent, and viscosity is low, and storage stability is good, has excellent curing rate, And the printing appearance after solidifying is good, adhesive force and wearability are excellent, odorlessness.

Specifically, radiation curing gravure ink composition of the invention, includes: (A) modified pigment, (B) cation are poly- Conjunction property compound, (C) free-radical polymerised compound, (D) cationic photoinitiator, and (E) radical photoinitiator.

Each component will more specifically be illustrated below.

<(A) modified pigment>

Pigment is the important component in gravure ink, it is dispersed in ink film forming matter with minimum particle, is mainly played The effect of color and covering.Since pigment additional amount is larger in ink, it to the storage stability of ink, viscosity, curing rate and Printing performance has larger impact.

Modified pigment in the present invention as component (A) is received including pigment and the inorganic oxide for being coated on surface of pigments Rice corpuscles；The DBP oil absorption of the modified pigment is 150-250ml/100g, and partial size is 0.01-1 μm, pH value 4.5-10.

Inventor surprisingly has found that face can be effectively prevent by carrying out the processing of inorganic oxide nanoparticles cladding to surface of pigments Material cohesion.Modified pigment can substantially improve its lipophilic and wettability, and can promote the stabilization of ink dispersion system Property.The oxide is selected from least one of silica, titanium dioxide, iron oxide, aluminium oxide.The pigment can be Machine pigment and inorganic pigment.Suitable organic pigment includes: azo (azo including bisazo and condensation), thioindigo, yin pellet Ketone, different indanthrone, anthracene form anthrone, anthraquinone, isoviolanthrone, three benzo dioxazines, quinoline a word used for translation diketone and phthalocyanine dye series.Preferably Organic pigment is that phthalocyanine dye (especially copper phthalocyanine), azo pigments, indanthrone, anthracene form anthrone and quinoline a word used for translation diketone.Properly Inorganic pigment include: carbon black, titanium dioxide, silica, aluminium oxide, iron oxide and sulfide.

Inventor has found in an experiment, the size of the height of modified pigment oil absorption and partial size to the tones of printed patterns and Printing appearance has a direct impact.It is measured referring to GB/T5211.15-1988 standard, the DBP oil absorption of modified pigment is with 150- 250ml/100g is advisable, preferably 200-250ml/100g.The suitable particle size range of modified pigment is 0.01-1 μm, preferably 0.1- 0.8μm。

The existing gravure ink in this field will not usually limit the pH value for including pigment.But researcher of the present invention It was found that ink is easy to appear gelatin phenomenon in storage tank as the PH of pigment used≤4, storage time can shorten；And work as pigment PH >=10 when, ink solidification speed is obviously prolonged.Therefore, inventor passes through many experiments and verifies repeatedly and determined suitably PH range, the pH value of the modified pigment are 4.5-10, preferably 5-9.

The factors such as pigment self property, surface state, processing conditions, surface treating agent have an impact to the pH value of pigment. The pH value of modified pigment is scattered in distilled water by referring to national standard GB/T1717-1986 in the present invention, measurement gained The pH value of solution determines.Specific measurement method includes: to prepare 10% (m/m) pigment suspension with distilled water in glass container Liquid clogs container with plug, and fierceness concussion 1min is then allowed to stand 5min, removes plug, measures the PH of suspension, be accurate to 0.1 Unit.

In radiation curing gravure ink composition of the invention, by percentage to the quality, the content of modified pigment is 2- 20%, preferably 5-15%.

<(B) cationically polymerizable compound>

The common cationically polymerizable compound in radiation curing field includes oxygen heterocycle butane, epoxies chemical combination Object and vinyl ethers compound.

In gravure ink composition of the invention, select oxygen heterocycle butane as cationically polymerizable compound It is advantageous to better curing rate is obtained.Meanwhile being considered based on physical characteristics such as printing appearance, substrate adhesions, preferably It is used cooperatively by oxygen heterocycle butane (B1) and epoxy compounds (B2).

Applicable oxygen heterocycle butane (B1), can be monofunctional compound, is also possible to polyfunctional compound. Simple function example includes (but not limited to this): 3- methyl -3- hydroxymethyl oxetane, 3- ethyl -3- hydroxymethyl oxa- Cyclobutane, 3- ethyl -3- (hexoxymethyl) oxetanes, 3- ethyl -3- (2- Ethylhexoxymethyl) oxetanes, 3- ethyl -3- [(phenoxy group) methyl] oxetanes, 3- ethyl -3- (chloromethyl) oxetanes, isobutoxymethyl (3- Ethyl -3- oxetanylmethyl) ether, isobornyl oxygroup ethyl (3- ethyl -3- oxetanylmethyl) ether, different ice Chip base (3- ethyl -3- oxetanylmethyl) ether, 2- ethylhexyl (3- ethyl -3- oxetanylmethyl) ether, second Base diethylene glycol (DEG) (3- ethyl -3- oxetanylmethyl) ether etc..Multifunctional example includes (but not limited to this): bis- [1- ethyls (3- oxetanyl)] methyl ether, bis- (chloromethyl) oxetanes of 3,3-, bis- (3- the oxetanyl) -5- oxa-s-of 3,7- Bis- [(3- ethyl -3- oxetanylmethoxy) methyl] ethane of nonane, 1,2-, the bis- [(3- ethyl -3- oxa- ring fourths of 1,3- Alkyl methoxyl group) methyl] propane, ethylene glycol bis- (3- ethyl -3- oxetanylmethyl) ethers, two methylene of tristane diyl Base (3- ethyl -3- oxetanylmethyl) ether, trimethylolpropane tris (3- ethyl -3- oxetanylmethyl) ether, Bis- [(3- ethyl -3- oxetanylmethoxy methoxyl group) methyl] benzene of 1,4-, 1,4- bis- (3- ethyl -3- oxetanylmethoxies) Bis- (3- ethyl -3- oxetanylmethoxy) hexanes of butane, the 1,6-, (3- ethyl -3- oxetanyl of pentaerythrite three Methyl) ether, pentaerythrite four (3- ethyl -3- oxetanylmethyl) ether, the bis- (3- ethyl -3- oxa- ring fourths of polyethylene glycol Alkyl methyl) ether, dipentaerythritol six (3- ethyl -3- oxetanylmethyl) ether, (3- ethyl -3- of dipentaerythritol five Oxetanylmethyl) ether, dipentaerythritol four (3- ethyl -3- oxetanylmethyl) ether etc..In addition, application No. is 201610548580.7,201610550205.6,201710706339.7 and 201710622973.2 Chinese patent application in Those disclosed oxygen heterocycle butane (herein by its full text be introduced into using as reference) can also be used in composition.

Consider from overall applicability performance, it is further preferred that oxygen heterocycle butane (B1) is selected from following compound At least one of.

As applicable epoxy compounds (B2), cycloaliphatic epoxy, hydrogenated epoxy compound, fragrance can be At least one of race's epoxide, aliphatic epoxy compound, preferably cycloaliphatic epoxy.

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, 4- vinyl -1- cyclohexene dicyclic oxide, bicyclic nonadiene Di-epoxide, 3,4- epoxycyclohexane carboxylate, 3,4- epoxycyclohexyl-methyl -3 ', 4 '-epoxycyclohexyl formic acid esters and oneself Polymerizate, the 4- methyl-1 of lactone, 2- 7-oxa-bicyclo[4.1.0,2,2- bis- (3,3 '-epoxycyclohexyl) propane, 2- (3,4- epoxy Hexamethylene) ethyl trimethoxy silane etc..

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..More preferable hydrogenated bisphenol A type ring Oxygen compound, A Hydrogenated Bisphenol A F type ring oxygen compound.

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..Wherein, more preferably bisphenol-A type ring Oxygen compound and fluorenes system epoxide.

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..Wherein, particularly preferably OGSOLEG-210。

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, intramolecular have different types of cationic polymerizable group compound can also be used as sun from Sub- polymerizable compound uses.For example, as having epoxy group (such as alicyclic epoxy group) and vinyl ethers simultaneously in the molecule Those of record compound in Japanese Unexamined Patent Publication 2009-242242 bulletin can be used in the example of base；As having simultaneously in the molecule There is the example of oxetanyl and vinyl ether group, those of record in Japanese Unexamined Patent Publication 2008-266308 bulletin can be used Compound.

Content of component (B) the cationically polymerizable compound in gravure ink can be needed according to substrate type and performance into The appropriate adjustment of row, is advisable with 30-80 mass %, preferably 40-70%.Wherein, oxygen heterocycle butane (B1) and epoxies The mass ratio of compound (B2) is preferably 2-5:1, more preferably 2-4:1.

<(C) free-radical polymerised compound>

Free-radical polymerised compound as component (C) is not particularly limited, as long as free radical polymerization can be carried out Compound.For example, (but not limited to this) can be enumerated: have (methyl) acryloyl group, (methyl) acryloxy, The chemical combination of the radically polymerizable groups such as (methyl) acrylamido, ethenyl aromatic yl, vinyl ether group, ethylene oxy carbonyl group Object.

Example as (methyl) acryl compound, comprising: 1- butylene -3- ketone, 1- penten-3-one, 1- hexene -3- Ketone, 4- phenyl -1- butylene -3- ketone, 5- phenyl -1- penten-3-one etc. and their derivative etc..

Example as (methyl) acryloyl-oxy based compound, comprising: (methyl) methyl acrylate, (methyl) acrylic acid second Ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, Tert-butyl Methacrylate, (methyl) acrylic acid-2-ethyl Own ester, (methyl) isodecyl acrylate, (methyl) acrylic acid n-dodecane base ester, (methyl) acrylic acid n-octadecane base ester, (first Base) acrylic acid n-butoxy ethyl ester, butoxy diethylene glycol (methyl) acrylate, methoxy triethylene (methyl) acrylic acid Ester, methoxy poly (ethylene glycol) (methyl) acrylate, (methyl) cyclohexyl acrylate, (methyl) the just own ester of acrylic acid, (methyl) Tetrahydrofurfuryl acrylate, (methyl) benzyl acrylate, (methyl) phenoxyethyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) third Olefin(e) acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, methacrylic acid, 2- methacryloxyethyl Succinic acid, 2- methacryloxyethyl hexahydro phthalic acid, 2- methacryloxyethyl -2- hydroxypropyl benzene diformazan Acid esters, (methyl) glycidyl acrylate, 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, 1,4-butanediol two (methyl) Acrylate, neopentyl glycol two (methyl) acrylate, 1,6- hexylene glycol two (methyl) acrylate, 1,9- nonanediol, two (first Base) acrylate, 1,10- decanediol two (methyl) acrylate, glycerol two (methyl) acrylate, 2- hydroxyl 3- acryloyl-oxy Base propyl (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, (methyl) acrylic acid trifluoro ethyl ester, (methyl) perfluoroethyl octyl ethyl ester, (methyl) isoamyl acrylate, the different tetradecane base ester of (methyl) acrylic acid, γ-(first Base) acryloyloxypropyltrimethoxysilane, isocyanic acid 2- (methyl) acryloyloxyethyl ester, isocyanic acid 1, the bis- (propylene of 1- Acyloxy) ethyl ester, isocyanic acid 2- (2- methacroyloxyethoxy) ethyl ester, vinyltrimethoxysilane, vinyl three Ethoxysilane, 3- (methyl) acryloxypropyl triethoxysilane etc. and their derivative etc..

Example as (methyl) acrylamide based compound, comprising: acrylic acid morpholine -4- base, acryloyl morpholine, N, N- Dimethylacrylamide, N, N- acrylamide, N methacrylamide, N- ethyl acrylamide, N- propyl acryloyl Amine, n-isopropyl acrylamide, N- butylacrylamide, N- n-butoxy methyl acrylamide, N- hexyl acrylamide, N- are pungent Base acrylamide etc. and their derivative etc..

As ethenyl aromatic yl, the example of vinyl ethers based compound, above-mentioned (B) cationically polymerizable compound can be enumerated In those of enumerate identical instances.

Compound as ethylene oxy carbonyl, comprising: formic acid isopropyl enester, methylvinyl acetate, propionic acid isopropyl enester, Butyric acid isopropyl enester, isobutyric acid isopropyl enester, caproic acid isopropyl enester, valeric acid isopropyl enester, isovaleric acid isopropyl enester, lactic acid isopropyl Enester, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, sad vinyl acetate, vinyl laurate, Pork and beans Cool vinyl acetate, vinyl palmitate, stearic acid vinyl ester, cyclohexane-carboxylic acid vinyl acetate, vinyl pivalate, sad second Enester, monochloro acetic acid vinyl acetate, vinyl hexanediacetate, vinyl methacrylate, Vinyl crotonate, sorbic vinyl Ester, vinyl benzoate, vinyl cinnamate etc. and their derivative.

Mass ratio of component (C) free-radical polymerised compound in radiation curing gravure ink composition of the invention be 10-50%, preferably 15-30%.

<(D) cation light initiator>

Component (D) cationic photoinitiator can be selected from one or both of salt compounded of iodine, sulfosalt, aryl cyclopentadienyl molysite with On combination.

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 (D) 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 (optionally) is by-O- ,-S- or 1,4- phenylene institute Replace；

R₃And R₄It is independently represented each other hydrogen, C₁-C₂₀Linear or branched alkyl group, C₄-C₂₀Cycloalkyl-alkyl or alkyl ring Alkyl, C₆-C₂₀Substituted or unsubstituted aryl, and the acyclic-CH in these groups₂Optionally by-O- ,-S- or 1,4- Replaced phenylene；

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 represent R₆And R₇Number, be selected from 0,1,2,3 or 4.

X^-It is independently represented each other M^-、ClO₄ ^-、CN^-、HSO₄ ^-、NO₃ ^-、CF₃COO^-、(BM₄)^-、(SbM₆)^-、(AsM₆)^-、 (PM₆)^-、Al[OC(CF₃)₃]₄ ^-, sulfonate ion, B (C₆M₅)₄ ^-Or [(Rf)_bPF_6-b]^-, wherein M be halogen (such as F, Cl, Br, I), Rf each independently represents the alkyl that >=80% hydrogen atom is replaced by fluorine atoms, and b indicates the integer of 1-5.

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 the cationic portion of above-mentioned salt compounded of iodine and sulfosalt photoinitiator can enumerate following knot Structure:

It is further preferred that the anion part of above-mentioned salt compounded of iodine and sulfosalt photoinitiator 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 ^-。

Commercially available cationic photoinitiator with homogeneous structure can also be used for component of the invention (D), such as (but it is unlimited In this): by Changzhou Tronly New Electronic Materials Co., Ltd. production PAG20001, PAG20002, PAG30201, PAG30101 etc., by the Irgacure250 etc. of BASF Corp. of Germany's production.

By percentage to the quality, component (D) cationic photoinitiator containing in gravure ink composition of the invention Amount is 1-20%, preferably 3-10%.

<(E) radical photoinitiator>

After determining component (C) free-radical polymerised compound, select applicable radical photoinitiator to ability It is relatively easy to for field technique personnel.In general, can attempt using those of in existing radical UV curing system There is photoinitiator, such as can be selected from benzoin class, acetophenones, Alpha-hydroxy ketone, alpha-amido ketone, acyl group phosphorous oxides, two One of Benzophenone class, 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 (E) in gravure ink composition of the invention is 1-20%, preferably 3-10%.

<(F) filler>

Optionally, radiation curing gravure ink composition of the invention also contains filler (F).The type of component (F) filler It is not particularly limited, those conventional use of types in gravure ink can be used.Typically, filler can be selected from nano-sized carbon At least one of sour calcium, aluminium hydroxide, barium sulfate, silica, talcum powder and kaolin.

By percentage to the quality, content of the component (F) in gravure ink composition is 0-20%, preferably 0-10%.

Other than said components (A)-(F), according to products application environment needs, gravure ink of the invention is also alternative Add organic and/or inorganic assistant commonly used in the art, including (but not limited to this) levelling agent, dispersing agent, curing agent, table in ground Face activating agent, defoaming agent, storage reinforcing agent etc., this is to be easy determination to those skilled in the art.With mass percent Meter, 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.The type of sensitizer can be pyrazoline compounds, acridine Close object, anthracene compound, naphthalene compounds, coumarin kind compound, tertiary amine compounds etc..As anthracene class sensitizer chemical combination Object, particularly preferably with the compound of 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 can be 0-5%, preferably 0-2%.

Under the radiation of the energy such as ultraviolet light, visible light, infrared ray, electron beam, laser, gravure ink of the invention occurs poly- Reaction is closed, to realize rapid draing.As the light source for assigning energy, preferably dominant wavelength is in the region of 250-450nm, example Including 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 quasi-molecule swash The various light sources such as light, Xe-F excimer laser, semiconductor excitation Solid State Laser.

Radiation curing gravure ink of the invention is can be obtained into the mixing of each component ingredient, specific preparation process can refer to spoke Those of penetrate in solidification composition filling field conventional method.Typically, preparation process includes: pigment modification processing, then in constant temperature Constant humidity and under conditions of avoiding radiating light source, ingredient is pre-dispersed, and grinding, (strainer filtering through predetermined size, is had for filtering There is the product of required partial size).

Radiation curing gravure ink composition storage stability of the invention is good, and viscosity is low, on the printer printability Good, metastatic is good, and curing rate is fast, can high speed printing, be suitable for a variety of substrates, especially suitable for paper, plastics, film etc. Carrier surface, the coating attachment fastness after solidification is strong, and wear-resisting property is excellent, and printing appearance is good, odorlessness, has very strong The 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 modified pigment

(1) inorganic modified pigment

Carbon black a-1 (Mitsubishi chemical Co., Ltd's system, MA100) after dry 3h, is ground at 60-70 DEG C in mortar Average grain diameter is to 0.3 μm or so.Then, it weighs 100g carbon black to be added in 1L flask, and 800ml deionized water is added, stirring is simultaneously Ultrasonic disperse is at uniform suspension.

Suspension is heated in thermostat water bath and is stablized at 65 DEG C or so, adjusts pH value to 9.

Weigh 11.8g Na₂SiO₃·9H₂O is dissolved in wiring solution-forming in 110ml water, is slowly dropped in flask, at the uniform velocity stirs It mixes, and is added dropwise within the scope of 10% hydrochloric acid adjusting pH value to 4-9 simultaneously.After being added dropwise, constant temperature stirs 30min.

Suspension is washed through filtering, deionized water after the reaction was completed, and dry 20min, obtains silica packet at 105 DEG C The black modified pigment A-1 covered.

After measured, the DBP oil absorption values of modified pigment A-1 are 220ml/100g, and average grain diameter is 0.46 μm, pH value 8.

Referring to the preparation method of A-1, the carbon black a-1 inorganic pigment for being substituted for other types is subjected to same oxide packet Modification is covered, corresponding modified pigment is obtained.It is as shown in the table:

Table 1

(2) organically-modified pigment

Take the hydrochloric acid that calcium chloride solution, 40g dehydrated alcohol and 20g mass fraction that 150g mass fraction is 20% are 10% Solution stirs 30min after mixing with 350r/min, adds 30g nano silica, dispersed after ultrasonic disperse 30min Liquid is passed through carbon dioxide gas into dispersion liquid and generates to without precipitating, filter residue is obtained by filtration after standing 8-10h, uses deionized water It is transferred in drying box after washing filter residue 3-5 times, dries at 105-110 DEG C to constant weight, obtain blotting ground.

10g blotting ground and 20g C.I. pigment Blue-61 (a-3) are taken, the sodium carbonate that 400g mass fraction is 5% is added to In solution, under 45 DEG C of waters bath with thermostatic control, for 24 hours with 350r/min stirring, load liquid is obtained.

100g butyl titanate, 1-2g silane coupling agent KH-560 and 200ml deionized water is added into load liquid, mixes 5h is stirred with 350r/min in 90 DEG C of waters bath with thermostatic control after closing uniformly, obtains coated by titanium dioxide organic pigment mixed liquor.

Cladded type organic pigment mixed liquor is placed in hydrothermal reaction kettle, insulation reaction 5h, is cooled to room temperature at 110 DEG C After filter cake is obtained by filtration, be washed with deionized filter cake 2 times and be transferred in drying oven, dry at 105 DEG C to constant weight, then will do Dry product, which is fitted into grinder, to be ground, and organically-modified pigment A-3 is obtained.

After measured, the DBP oil absorption values of modified pigment A-3 are 225ml/100g, and average grain diameter is 0.56 μm, and pH value is 5.5。

Referring to the preparation method of A-3, the a-3 organic pigment for being substituted for other types is subjected to same oxide cladding and is changed Property processing, obtain corresponding modified pigment.It is as shown in the table:

Table 2

2, the preparation of radiation curing gravure ink

It is formulated according to shown in table 3, raw material is at the uniform velocity stirred 1 hour using high-speed mixer under the conditions of yellow fluorescent lamp, so Ground afterwards 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 mass fraction.

Table 3

In table 3, each component concrete meaning is as follows:

Modified pigment: the meaning as shown in the preparation of modified pigment " 1, "；

B1-1:

B1-2:

B1-3:

B1-4:

B1-5:

B2-1:3,4- epoxycyclohexyl-methyl -3 ', 4 '-epoxycyclohexyl formic acid esters, Jiangsu Tai Teer new material science and technology have Limit company；

B2-2: bis- ((3,4- epoxycyclohexyl) methyl) adipate esters, Jiangsu Tai Teer new material Science and Technology Ltd.；

B2-3:4- vinyl -1- cyclohexene dicyclic oxide；

C-1: trimethylolpropane trimethacrylate, Sartomer；

C-2: tripropylene glycol diacrylate, Sartomer；

D-1: bis- (4- (diphenyl sulfonium) phenyl) bis- hexafluorophosphates of thioether-and 4- (thiophenyl) phenyl diphenyl sulphur hexafluoro Phosphate；

D-2:

D-3:

D-4:

E-1:2- methyl-1-[4- (methyl thio) phenyl]-2- (4- morpholinyl)-1- acetone, BASF Corp. of Germany；

E-2:2- hydroxy-2-methyl -1- phenyl -1- acetone, BASF Corp. of Germany；

E-3:1- hydroxycyclohexyl phenyl ketone, BASF Corp. of Germany；

F-1: silica A-200, Germany wins wound Degussa Specialty Chemical Co., Ltd；

F-2: titanium dioxide R706, Dupont；

F-3: calcium carbonate SW-01, Polyplastics Co., Ltd.；

G1-1:

G1-2:

G1-3:

G2:BYK 333, Germany win wound Degussa Specialty Chemical Co., Ltd；

G3: hindered nitroxyl stabilizers

3, gravure 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, to the sample of embodiment and comparative example It is tested for the property and evaluates.

(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 13217.3-2008 gravure ink viscosity test standard, ink viscosity is tested, unit s.

(2) storage stability is tested

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%.

(3) curing and drying 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.

Evaluation result is summarized in table 4.

4, printing performance test and evaluation

(the embodiment: 230m/min under the conditions of ensuring that dry most slow linear velocity can be fully cured in gravure ink；Comparison Example: 160m/min), gravure ink is printed on PET film substrate, thickness is about 10 μm, and after placing for 24 hours, printing product is i.e. solid The physical property for changing coating is tested and is evaluated, including attachment fastness, wearability and printing appearance.

(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 Meet under the sight sample light source of 3 defined of CY/T, is 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；Otherwise appoint What one undesirable, is denoted as unqualified.

Evaluation result is summarized in table 4.

Table 4

Radiation curing gravure ink composition viscosity of the invention is low it can be seen from the evaluation result of table 4, stable storing Property it is high, and there is the curing rate being obviously improved.Coating after solidification is wear-resisting and adhesion property is very excellent, and printing pattern is whole Clean, the smooth of the edge is good colour, has embodied fabulous application performance.

5, performance is further tested and is evaluated

Radiation curing gravure ink composition of the invention is respectively applied to paper and plastic film substrate, is applied to Performance makees 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 is applied to paper substrate is evaluated.

Gravure ink composition is prepared by formula in table 5, it will be oily by the solvent-free intaglio press of loose moral (model: A380) Ink print carries out radiation curing, line on meeting 10335.1 printing rubber millboard of GB/T, using high-pressure sodium lamp (RW-UV.70201) Power is 80W/cm, obtains the printed patterns that thickness is about 10 μm.

Referring to evaluation method hereinbefore, to the viscosity of printing ink composition, storage stability and curing and drying speed, and Coating attachment fastness, wearability and printing appearance are evaluated.

Test result is compiled in table 5.

Table 5

(2) plastic film substrate

Referring to being wanted in QB/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 of the present invention is evaluated respectively.

Gravure ink composition is prepared by formula in table 6.It will be oily by the solvent-free intaglio press of loose moral (model: A380) Ink is respectively printed on PET, PVC, PP and PE substrate, using wavelength for 395nm LED light as radiating light source, the intensity of light source is 15w/cm², obtain the printed patterns that thickness is about 10 μm.

Referring to evaluation method hereinbefore, to the viscosity of printing ink composition, storage stability and curing and drying speed, and Coating attachment fastness, wearability and printing appearance on different plastic film substrates are evaluated.

Test result is compiled in table 6.

Table 6

In terms of from the test result of table 5 and table 6, the radiation curing gravure ink composition energy of the invention containing modified pigment Enough it is applied to different substrate materials surface, and all has excellent performance.

Claims

1. a kind of radiation curing gravure ink composition, includes: (A) modified pigment, (B) cationically polymerizable compound, (C) from By base polymerizable compound, (D) cationic photoinitiator, and (E) radical photoinitiator.

2. radiation curing gravure ink composition according to claim 1, it is characterised in that: component (A) modified pigment packet It includes pigment and is coated on the inorganic oxide nanoparticles of surface of pigments；And the DBP oil absorption of the modified pigment is 150- 250ml/100g, partial size are 0.01-1 μm, pH value 4.5-10.

3. radiation curing gravure ink composition according to claim 2, it is characterised in that: the oxide is selected from two At least one of silica, titanium dioxide, iron oxide, aluminium oxide.

4. radiation curing gravure ink composition according to claim 2, it is characterised in that: the DBP oil suction of modified pigment Amount is 200-250ml/100g, and partial size is 0.1-0.8 μm.

5. radiation curing gravure ink composition according to claim 2, it is characterised in that: the pH value of modified pigment is 5- 9。

6. radiation curing gravure ink composition according to claim 1, it is characterised in that: component (B) cationic polymerization Property compound is made of oxygen heterocycle butane (B1) and epoxy compounds (B2).

7. radiation curing gravure ink composition according to claim 6, it is characterised in that: the epoxy compounds It (B2) is cycloaliphatic epoxy, preferably with the epoxide of epoxycyclohexyl.

8. radiation curing gravure ink composition according to claim 6 or 7, it is characterised in that: oxetanes class The mass ratio for closing object (B1) and epoxy compounds (B2) is 2-5:1, preferably 2-4:1.

9. radiation curing gravure ink composition according to claim 1, it is characterised in that: component (C) free radical polymerization Property compound be selected from (methyl) acryloyl group, (methyl) acryloxy, (methyl) acrylamido, ethenyl aromatic yl, At least one of the compound of the radically polymerizable groups such as vinyl ether group, ethylene oxy carbonyl group.

10. radiation curing gravure ink composition according to claim 1, it is characterised in that: component (D) cationic light Initiator is selected from the combination of one or more of salt compounded of iodine, sulfosalt, aryl cyclopentadienyl molysite.

11. radiation curing gravure ink composition according to claim 1, it is characterised in that: component (E) free radical type light Initiator is selected from benzoin class, acetophenones, Alpha-hydroxy ketone, alpha-amido ketone, acyl group phosphorous oxides, benzophenone, sulphur One of miscellaneous anthrone class, Anthraquinones, oxime ester lightlike initiating agent are a variety of.

12. radiation curing gravure ink composition according to claim 1, it is characterised in that: also contain (F) filler.

13. radiation curing gravure ink composition according to claim 1, it is characterised in that: also contain sensitizer, preferably It is anthracene class sensitizer.

14. radiation curing gravure ink composition answering on paper, plastics, film of any of claims 1-13 With.