CN110964383A

CN110964383A - Radiation curing composition

Info

Publication number: CN110964383A
Application number: CN201811590403.0A
Authority: CN
Inventors: 钱彬; 杨金梁; 严春霞
Original assignee: Changzhou Green Photosensitive Materials Co ltd
Current assignee: Changzhou Green Photosensitive Materials Co ltd
Priority date: 2018-09-30
Filing date: 2018-12-25
Publication date: 2020-04-07

Abstract

The invention discloses a pigment dispersion, application of the pigment dispersion and a radiation curing composition containing the pigment dispersion. The radiation curable composition does not require the use of a volatile solvent, is environmentally friendly, has excellent applicability to printing on plastic films, can be cured quickly to exhibit excellent production efficiency, and can form a multifunctional cured layer after curing, which is excellent in chemical resistance, scratch resistance, adhesion to various substrates, trackability during shrinkage, and the like.

Description

Radiation curing composition

Technical Field

The invention relates to the technical field of pigment and radiation curing, in particular to a pigment dispersion, application thereof in a radiation curing composition and the radiation curing composition containing the pigment dispersion.

Background

Plastic labels are generally attached to the surfaces of plastic bottles (such as PET bottles and the like), metal bottles (such as iron cans, aluminum cans and the like), glass bottles (tea beverages and the like), and the like, which are widely used as liquid containers on the market, for indication or decorative purposes, and among such plastic labels, shrink labels or stretch labels having good decorativeness and processability are often used, and the production of these labels generally involves coating or printing a composition on the surface to impart functions such as decorativeness, good processability, and the like by printing a pattern.

Existing printing compositions typically contain large amounts of organic solvents, and the production process involves evaporation of the solvent, which requires high environmental costs and is therefore not appreciated. The aqueous composition of the solvent-based composition has a problem of low production efficiency due to a low printing speed. In order to satisfy the requirements of environmental protection and high production efficiency, compositions containing an epoxy resin as a base resin and using substantially no solvent have been developed and improved in the art, but there are also disadvantages in terms of post-performance, such as good adhesion to only a single base material, etc.

Disclosure of Invention

The invention aims to provide a pigment dispersion, application of the pigment dispersion and a radiation curing composition containing the pigment dispersion.

The radiation-curable composition using the pigment dispersion is environmentally friendly without using a volatile solvent, has excellent applicability to printing on plastic films, can be cured quickly to exhibit excellent production efficiency, and can form a multifunctional cured layer after curing, which is excellent in chemical resistance, scratch resistance, fastness of adhesion to various substrates, trackability during shrinkage, and the like.

Detailed Description

In order to more fully describe the invention, various aspects of the invention are described in more detail below.

< pigment Dispersion >

The pigment dispersion of the present invention comprises: pigment, dispersing auxiliary agent and dispersing monomer.

Different from the prior art, the invention carries out targeted improvement on the pigment form, and the pigment form is presented in the form of a preformed pigment dispersion, thereby bringing better dispersibility to a composition system and further improving the overall application performance.

The pigment is not particularly limited in kind, and may be selected from inorganic pigments and organic pigments, and any pigment used in conventional compositions can be used.

Illustratively, the inorganic pigment may be selected from or include at least one of: carbon black, titanium dioxide, aluminum oxide, red iron oxide, yellow iron oxide, iron blue, phthalocyanine blue and brown iron oxide. The carbon black may be at least one of furnace black, pyrolytic carbon black, acetylene black, or channel black.

Illustratively, the organic pigment may be selected from or include at least one of: azo pigments, diazo pigments, phthalocyanine pigments, anthraquinone pigments, quinophthalone pigments, thioindigo, indanthrone, anthraquinophthalone, isoviolanthrone.

Illustratively, the above-mentioned pigment may also be selected from or include at least one of the following: pigment yellow 3, yellow12, yellow 13, yellow 14, yellow 17, yellow 55, yellow 81, yellow 83, yellow 97, yellow 110, yellow 138, yellow 154, yellow 168, yellow 174, yellow 176, yellow 183, yellow 188, yellow 191, yellow1, yellow 62, yellow 65, yellow 74, yellow 139, yellow 150, yellow 151, yellow 180, yellow 184; pigment red 2, red 8, red 21, red 48: 1. red 48:2, red 48:3, red 48:4, red 52:1, red 52:2, red 53:1, red 53:2, red 112, red144, red 146, red 166, red 169, red 184, red 202, red 254, red 269, red 3, red 22, red49:1, red49: 2, red 57:1, red 81, red 122, red 149, red 176, red 177, red 179, red185, red 208, red 266, red 268, red 170, red 269; pigment orange 13, orange 34, orange36, orange 5, orange 16, orange 73; pigment violet 23, violet 27, violet 1, violet 3, violet 19; pigment green 7, green 36; pigment blue 15:1, blue 79, blue 15:0, blue 15:2, blue 15:3, blue 15:4, blue 15:6, blue 27, blue 60; orion sb4a, cabot 935, mitsubishi carbon blacks (#2650, #2600, #2350, #2300, #1000, #980, #970, #960, #950, #900, #850, #750B, #650B, MCF88, MA 600).

The dispersing aid is selected from or includes a silicon-containing compound.

Typically, the above-mentioned dispersing aid may be selected from or include at least one of the following: KH570, KH560, KH550, A-151, A-132, Solsperse 24000, Solsperse 28000, Solsperse32000, Solsperse36000, Solsperse85000, Solsperse 86000. These dispersing aids are commercially available.

As the dispersing assistant, the silicon-containing epoxy resin can be selected or included, and the silicon-containing epoxy compound has a structure shown in the following structural general formula (I):

wherein,

R₀₁each independently is an oxetanyl or oxiranyl group which is

The oxirane group-containing group is an oxirane alkoxy group (preferably C terminally substituted with an oxirane group)₁-C₅Alkoxy groups of (ii);

R₀₂is C₁-C₅Straight or branched alkyl of (2), C₁-C₅A straight or branched alkoxy group of (a);

p is an integer from 1 to 3, q is an integer from 1 to 3, and p + q is 4;

R₀₃is represented by C₁-C₁₀OfChain or branched alkyl, C₂-C₃₀Alkenyl of (a), and R₀₃In (C-CH)₂Optionally substituted by-O-, -COO-, -OCO-or

Substituted; and optionally, R₀₃The hydrogen atoms in (a) may each independently be substituted with alkyl, halogen, or nitro;

R₀₄is methyl or ethyl;

q represents C₁-C₅A straight or branched trivalent alkyl group of (1), wherein-CH₂-may be optionally substituted by-O-, -COO-, -OCO-.

Further, the silicon-containing epoxy compound may be a compound of the following structure:

the silicon-containing epoxy compound can be prepared by taking tetramethyl silicate, tetraethyl silicate or tetrabutyl silicate as raw materials and reacting the raw materials with R₀₁-OH (i.e. hydroxyl-containing oxetane monomer and/or oxirane monomer) is subjected to transesterification reaction, and the obtained product is obtained by controlling the raw material ratio.

On the basis of the structural general formula (I), the dispersing aid can also be selected from or comprise at least one of fluorine-containing silicon-containing epoxy compounds shown in the following structures:

the fluorine-containing silicon-containing epoxy compound can be synthesized by reacting fluorine-containing organic alcohol with TCM207 (Tronly, a product of Changzhou powerful new electronic materials Co., Ltd.) to obtain a fluorine-containing hydroxyl-containing oxetane monomer, and then carrying out transesterification reaction with tetramethyl silicate or tetraethyl silicate.

The dispersing monomer can be selected from or include the compounds represented by the general structural formula (I) with the proviso that R is₀₂Is C₁-C₅Linear or branched alkyl.

Illustratively, the above-mentioned dispersing monomer may be selected from or include at least one of:

the dispersion monomers exemplified above are commercially available; or methyl chlorosilane (such as trimethyl chlorosilane, triethyl chlorosilane, dimethyl dichlorosilane and diethyl dichlorosilane) can be used as raw material to react with R₀₁Etherification of-OH (i.e. hydroxyl-containing oxetane monomer and/or oxirane monomer) withAlkali (such as sodium carbonate) is used as an acid-binding agent, the reaction is carried out for 2 to 3 hours at the temperature of between 0 and 15 ℃, and the proportion of the raw materials is controlled to obtain the dispersed monomer.

As dispersing monomers, it is also possible to select or to include other oxetane-group-containing and/or epoxy-group-containing compounds. Further, at least one selected from or including TCM series products made by Tronly, Celloxide 2021, UVR6110, UVR6100, UVR6105, UVR6107 and UVR 6128; preferably at least one of the TCM101, TCM103, TCM104, TCM105, TCM201, TCM207ME, TCM 209.

In the pigment dispersion of the present invention, the amounts of the pigment and the dispersing monomer added are 30 to 50 parts and 50 to 70 parts, respectively, based on 100 parts by mass of the total amount of the pigment and the dispersing monomer. The addition amount of a single dispersing aid is 0.1-0.3 time of the addition amount of the pigment.

In accordance with the above pigment dispersion, the present invention provides a method for producing a pigment dispersion, comprising the steps of:

(1) weighing the pigment, the dispersing auxiliary agent and the dispersing monomer according to the proportion for later use;

(2) adding a dispersing auxiliary agent into a dispersing monomer, stirring by using a homogenizer until the dispersing auxiliary agent is uniformly dispersed, adding the pigment and the dispersing beads within 10min, then continuing stirring until the cumulative particle size distribution D90 and the pH value of the pigment dispersion meet the requirements, stopping stirring, and filtering the dispersing beads to obtain the pigment dispersion.

As a medium used in the dispersion treatment, the dispersion beads may be selected from: ceramic microspheres such as zirconia, polymer spheres such as polyethylene and nylon, and metal spheres. From the viewpoint of abrasion resistance, the dispersed beads are preferably zirconia microspheres. The diameter of the dispersed beads is preferably 0.003 to 0.5mm, more preferably 0.01 to 0.45mm, and when the diameter is in this range, the pigment can be sufficiently finely divided. The ratio of the total amount of the pigment dispersion to the amount of the dispersing beads is preferably 1: 1-2.

In the technical scheme of the invention, D90 and pH value are key factors influencing the application performance of the pigment dispersion. The pigment dispersion preferably has a D90 value of 0.8 to 2 μm, preferably 0.8 to 1.8 μm, more preferably 0.8 to 1.5 μm, from the viewpoint of the balance of the prevention of the increase in viscosity and the improvement in storage stability; the pH of the pigment dispersion should be 4 to 10, preferably 5 to 10, more preferably 5.5 to 9.5, and further preferably 6 to 8.

The pigment dispersions of the invention can be used in any type of composition known in the art, in particular solvent-free composition systems, such as inks for flexographic, letterpress, intaglio, screen printing, thermal transfer printing, lithographic, digital printing or ink jet printing. Compared with the direct use of the pigment in the composition, the application form of the pigment dispersion can bring about better system dispersibility, so that the composition has better storage stability and has advantages in the aspects of print appearance, adhesion and the like. As a result, the present invention can obtain higher pattern quality under the same conditions.

< radiation curable composition >

The present invention also relates to the use of the above pigment dispersant in a composition, and a composition comprising the above pigment dispersion, resulting from the excellent properties exhibited by the pigment dispersion of the present invention when applied to the composition.

In the technical solution of the present invention, the photosensitive composition that can include the above-mentioned pigment dispersion as a component may be any one of the compositions in the prior art, and exemplarily, the present invention provides a radiation curable composition (also referred to as radiation curable ink) including the above-mentioned pigment dispersion (a), the cationically polymerizable compound (B), and the cationic photoinitiator (C), wherein the mass ratio of the pigment, the cationically polymerizable compound (B), and the cationic photoinitiator (C) in the pigment dispersion (a) is preferably (5 to 40): (50-85): (4-10).

The pigment dispersion (a) is as described above, and will not be repeated here. The other components included in the radiation-curable composition are specifically described below.

Cation polymerizable Compound (B)

As a film-forming component of the radiation-curable composition, the cationically polymerizable compound (B) may be selected from or include: oxetane compounds, epoxy compounds and vinyl ether compounds. In the composition of the present invention, it is advantageous to use an oxetane compound as the polymerizable compound for obtaining a higher curing rate. In addition, the cationically polymerizable compound (B) is preferably used in combination with an oxetane compound (B1) and an epoxy compound (B2) in view of physical properties such as appearance of printed products and adhesion to substrates.

The oxetane compound (B1) may be used singly or in combination of two or more.

Examples of monofunctional functions include (but are not limited to): 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- [ (phenoxy) methyl ] oxetane, 3-ethyl-3- (chloromethyl) oxetane, 3-ethyl-3- (cyclohexyloxymethyl) oxetane, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, and mixtures thereof, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, and the like.

Examples of multifunctional groups include (but are not limited to): bis [ 1-ethyl (3-oxetanyl) ] methyl ether, 3-bis (chloromethyl) oxetane, 3, 7-bis (3-oxetanyl) -5-oxa-nonane, 1, 2-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ethane, 1, 3-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1, 4-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] benzene, p-xylylene (3-ethyl-3-oxetanylmethyl) ether, p-xylylene, 1, 4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1, 6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetra (3-ethyl-3-oxetanylmethyl) ether, and the like.

Oxetane compounds such as those disclosed in chinese patent application nos. 201610548580.7, 201610550205.6, 201710706339.7, 201710622973.2, 201710035210.8, 201710035435.3, which are incorporated herein by reference in their entirety, are useful in the above compositions of the present invention. Commercial products such as: OXT-101, OXT-211, OXT-121, OXT-221, OXT-212, etc. of Toagosei can be used in the composition.

The epoxy compound (B2) may be at least one of an alicyclic epoxy compound, a hydrogenated epoxy compound, an aromatic epoxy compound and an aliphatic epoxy compound.

The "alicyclic epoxy compound" as used herein means a compound having an alicyclic epoxy group. From the viewpoint of further improving the curing speed, it is conceivable to use a polyfunctional alicyclic epoxy compound having 2 or more alicyclic epoxy groups in the molecule, or an alicyclic epoxy compound having 1 alicyclic epoxy group in the molecule and having an unsaturated double bond group such as a vinyl group, or a compound having a glycidyl group, or an epoxy compound having two or more epoxy groups.

As the above-mentioned alicyclic epoxy compound, preferred are epoxy compounds having an epoxycyclohexyl group, such as 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexylcarboxylate, ε -caprolactone-modified-3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexylcarboxylate, bis ((3, 4-epoxycyclohexyl) methyl) adipate, epoxycyclohexane, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 3, 4-epoxycyclohexylmethyl methacrylate, 3, 4-epoxycyclohexylmethacrylate, 1, 2-epoxy-4-vinylcyclohexane, 4-vinyl-1-cyclohexene diepoxide, bicyclononene diepoxide, bicyclohexyl-oxide, bicyclohexyl-ether, bicyclohexyl-, 3, 4-epoxycyclohexanecarboxylate, a polymerization product of 3, 4-epoxycyclohexylmethyl-3 ', 4 ' -epoxycyclohexylformate and caprolactone, 4-methyl-1, 2-epoxycyclohexane, 2-bis (3,3 ' -epoxycyclohexyl) propane, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane and the like.

The hydrogenated epoxy compound is preferably a compound having a glycidyl ether group directly or indirectly bonded to a saturated aliphatic cyclic hydrocarbon skeleton, and a polyfunctional glycidyl ether compound is suitable. Such a hydrogenated epoxy compound is preferably a completely or partially hydrogenated product of an aromatic epoxy compound, more preferably a hydrogenated product of an aromatic glycidyl ether compound, and still more preferably a hydrogenated product of an aromatic polyfunctional glycidyl ether compound. Specifically, it can be selected from hydrogenated bisphenol a type epoxy compounds, hydrogenated bisphenol S type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, and the like.

The aromatic epoxy compound is a compound having an aromatic ring and an epoxy group in a molecule, and the aromatic epoxy compound may be an epoxy compound having an aromatic ring conjugate system such as a bisphenol skeleton, a fluorene skeleton, a biphenyl skeleton, a naphthalene ring, or an anthracene ring; the compound in which the epoxy group in the aromatic epoxy compound is a glycidyl group is preferably a compound in which the epoxy group is a glycidyl ether group (i.e., an aromatic glycidyl ether compound), and the aromatic epoxy compound preferably includes a bisphenol a type epoxy compound, a bisphenol F type epoxy compound, a fluorene type epoxy compound, an aromatic epoxy compound having a bromine substituent, and the like.

The aromatic glycidyl ether compound may be an Epi-bis type glycidyl ether epoxy resin, a high molecular weight Epi-bis type glycidyl ether epoxy resin, a novolak, an aralkyl type glycidyl ether epoxy resin, or the like. The Epi-bis type glycidyl ether type epoxy resin may be a resin obtained by a condensation reaction of bisphenol such as bisphenol a, bisphenol F, bisphenol S, fluorene bisphenol and epihalohydrin. The high molecular weight Epi-bis type glycidyl ether epoxy resin may be a resin obtained by addition reaction of the Epi-bis type glycidyl ether epoxy resin with a bisphenol such as bisphenol a, bisphenol F, bisphenol S, and fluorene bisphenol. As the above aromatic glycidyl ether compound, preferable examples include: bisphenol A type compounds such as 828EL, 1003 and 1007 produced by epoxy resin Co., Ltd., and fluorene type compounds such as ONCOATEX-1020, ONCOATEX-1010, OGSOLEG-210 and OGSOLLPG produced by OSAKAGAS CHEMICALS.

The above aliphatic epoxy compound is a compound having an aliphatic epoxy group, such as an aliphatic glycidyl ether type epoxy resin. Preferred examples of the aliphatic glycidyl ether type epoxy resin include, but are not limited to, resins obtained by condensation reaction of a polyhydric compound, which may be selected from ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, glycerol, diglycerol, tetraglycerol, polyglycerols, trimethylolpropane and polymers thereof, pentaerythritol and polymers thereof, mono/polysaccharides (such as glucose, fructose, lactose, maltose, etc.), and the like, with epihalohydrin. Among them, an aliphatic glycidyl ether type epoxy resin having a propylene glycol skeleton, an alkylene skeleton, and an alkylene oxide skeleton in the central skeleton is more preferable.

Examples of the above vinyl ether compounds include: aryl vinyl ethers such as phenyl vinyl ether; alkyl vinyl ethers such as n-butyl vinyl ether and n-octyl vinyl ether; cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; hydroxyl-containing vinyl ethers such as 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether and 2-hydroxybutyl vinyl ether; and polyfunctional vinyl ethers such as hydroquinone divinyl ether, 1, 4-butanediol divinyl ether, cyclohexane divinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

In addition to the above, I47 to I56 in the structural formula (I) can also be used as the cationically polymerizable compound (B) according to the present invention. Further, compounds having different kinds of cationically polymerizable groups in the molecule can also be used as the polymerizable compound of the present invention. For example, as examples having both an epoxy group (e.g., alicyclic epoxy group) and a vinyl ether group in the molecule, those described in japanese patent laid-open No. 2009-242242; as examples of compounds having both an oxetanyl group and a vinyl ether group in the molecule, those described in Japanese patent laid-open No. 2008-266308 can be used.

The content of the cationically polymerizable compound (B) in the composition can be adjusted as appropriate depending on the kind of the base material and the performance requirements. When the oxetane compound (B1) and the epoxy compound (B2) are used in combination, the mass ratio of the oxetane compound (B1) to the epoxy compound (B2) is preferably (2-5):1, more preferably (2-4.5): 1.

Cationic photoinitiator (C)

The cationic photoinitiator (C) may be one or a combination of two or more selected from iodonium salts, sulfonium salts, and arylferrocenium salts. From the viewpoint of cost, effect of compounding use such as photoinitiation efficiency, curing speed and the like, iodonium salt and/or sulfonium salt type photoinitiators are preferred, and compounds having a structure represented by the following formula (II) and/or (III) are particularly preferred:

wherein R is₁And R₂Each independently represents hydrogen, C₁-C₂₀Straight or branched alkyl of (2), C₄-C₂₀Cycloalkylalkyl or alkylcycloalkyl of (A), and acyclic-CH in these groups₂-optionally substituted by-O-, -S-or 1, 4-phenylene;

R₃and R₄Each independently represents hydrogen, C₁-C₂₀Straight or branched alkyl of (2), C₄-C₂₀Cycloalkylalkyl or alkylcycloalkyl, C₆-C₂₀Substituted or unsubstituted aryl of (a), and acyclic-CH in these radicals₂-optionally substituted by-O-, -S-or 1, 4-phenylene;

R₅represents C₆-C₂₀Substituted or unsubstituted aryl of (1), C₆-C₂₀Substituted or unsubstituted alkylaryl of, C₁-C₂₀Straight or branched alkyl of (2), C₄-C₂₀Cycloalkylalkyl or alkylcycloalkyl, substituted or unsubstituted phenylthiophenyl, and the acyclic-CH in these groups₂-optionallySubstituted by carbonyl, -O-, -S-or 1, 4-phenylene;

R₆and R₇Each independently represents an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, a substitutable amino group, a cyano group, a nitro group, or a halogen atom;

m₁、m₂each represents R₆And R₇The number of (a) is selected from 0, 1,2, 3 or 4.

X^-Each independently represents M^-、ClO₄ ^-、CN^-、HSO₄ ^-、NO₃ ^-、CF₃COO^-、(BM₄)^-、(SbM₆)^-、(AsM₆)^-、(PM₆)^-、Al[OC(CF₃)₃]₄ ^-Sulfonate ion, B (C)₆M₅)₄ ^-Or [ (Rf)_bPF_6-b]^-Wherein M is a halogen (e.g., F, Cl, Br, I), Rf each independently represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, and b represents an integer of 1 to 5.

As a preferred structure, compounds having the structures represented by the formulae (II) and (III):

R₁and R₂Each independently represents hydrogen, C₁-C₁₂Straight or branched alkyl of (2), C₄-C₁₀Cycloalkylalkyl or alkylcycloalkyl of (A), and acyclic-CH in these groups₂-is optionally substituted by-O-;

R₃and R₄Each independently represents hydrogen, C₁-C₁₀Straight or branched alkyl of (2), C₄-C₁₀Cycloalkylalkyl or alkylcycloalkyl, C₆-C₁₂And a substituted or unsubstituted aryl group of (A), and the acyclic-CH in these groups₂-optionally substituted by-O-, -S-or 1, 4-phenylene;

R₅represents C₆-C₁₀Substituted or unsubstituted aryl of (1), C₆-C₁₀Substituted or unsubstituted alkylaryl, substituted or unsubstituted thiophenylphenyl, and the acyclic-CH in these groups₂-optionally substituted by carbonyl, -O-, -S-or 1, 4-phenylene;

R₆and R₇Is represented by C₁-C₁₀Straight or branched alkyl of (2), C₁-C₁₀Linear or branched alkoxy of (C)₁-C₁₀Alkylcarbonyl and halogen.

More preferably, the cationic moiety of the iodonium salt and sulfonium salt photoinitiators has the following structure:

more preferably, the anionic moiety of the iodonium salt and sulfonium salt photoinitiators is selected from the group consisting of: 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, commercially available cationic photoinitiators having the same structure may also be used as the cationic photoinitiator (C), for example (but not limited thereto): PAG20001, PAG20002, PAG30201, PAG30101 and the like by Tronly, Irgacure250 and the like by BASF, Pasteur, Germany.

In another embodiment of the present invention, the radiation-curable composition further includes a radical polymerizable compound (D) and a radical photoinitiator (E) in addition to the pigment dispersion (a), the cation polymerizable compound (B), and the cation photoinitiator (C). The ratio of the pigment, the cationically polymerizable compound (B), the cationic photoinitiator (C), the radically polymerizable compound (D), and the radical photoinitiator (E) in the pigment dispersion (a) is preferably (5 to 40): (39-74): (3-7): (16-50): (2-5).

The components (D) and (E) are specifically described below.

Radical polymerizable Compound (D)

The radical polymerizable compound (D) is not particularly limited as long as it is a compound capable of radical polymerization. For example, there may be mentioned (but not limited to): and compounds having a radical polymerizable group such as a (meth) acryloyl group, a (meth) acryloyloxy group, a (meth) acrylamido group, a vinyl aryl group, a vinyl ether group, or a vinyloxycarbonyl group.

Examples of the (meth) acryloyl compound include: 1-buten-3-one, 1-penten-3-one, 1-hexen-3-one, 4-phenyl-1-buten-3-one, 5-phenyl-1-penten-3-one and the like, and derivatives thereof and the like.

Examples of the (meth) acryloyloxy compound include: methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl methacrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, n-butoxyethyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, n-hexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methacrylic acid, 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropylphthalate, glycidyl (meth) acrylate, 2-methyl-2-acrylic acid-2- (phosphonooxy) ethyl ester, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, glycerol di (meth) acrylate, 2-hydroxy 3-acryloyloxypropyl (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, isoamyl (meth) acrylate, isotetradecyl (meth) acrylate, γ - (meth) acryloyloxypropyltrimethoxysilane, 2- (meth) acryloyloxyethyl isocyanate, 1-bis (acryloyloxy) ethyl isocyanate, 2- (2-methacryloyloxyethoxy) ethyl isocyanate, vinyltrimethoxysilane, vinyltriethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, etc., and derivatives thereof, and the like.

Examples of the (meth) acrylamido compound include: acrylic acid morpholin-4-yl, acryloyl morpholine, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-N-butoxymethylacrylamide, N-hexylacrylamide, N-octylacrylamide, and the like, and derivatives thereof, and the like.

Examples of the vinyl aryl group and vinyl ether group compounds include those exemplified as the cationic polymerizable compound (B).

As the compound of ethyleneoxycarbonyl group, there are included: isopropenyl formate, isopropenyl acetate, isopropenyl propionate, isopropenyl butyrate, isopropenyl isobutyrate, isopropenyl hexanoate, isopropenyl valerate, isopropenyl isovalerate, isopropenyl lactate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl octanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl pivalate, vinyl octanoate, vinyl monochloroacetate, divinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate, vinyl cinnamate, and the like, and derivatives thereof.

Free radical photoinitiator (E)

After the free radical polymerizable compound (D) is determined, at least one of the existing photoinitiators in the existing free radical photocuring system, such as benzoin, acetophenone, α -hydroxy ketones, α -amino ketones, acyl phosphorus oxides, benzophenones, thioxanthones, anthraquinones, and oxime ester photoinitiators, may be used, illustratively, the free radical photoinitiator (E) in the technical solution of the present invention may be selected from or include products sold under the trade names Irgacure 651, Irgacure184, Irgacure 907, Irgacure 369, Irgacure 500, Irgacure 1000, Irgacure819, Irgacure 261, Irgacure 784, Irgacure1173, Irgacure 2959, Irgacure 4265, and Irgacure 4263 by BASF corporation, products sold under the trade names SR1137, SR1136, SR1135, SR1125, etc. by Saedor corporation.

Filler (F)

Optionally, the radiation-curable composition of the invention may also comprise a filler (F). The type of the filler (F) is not particularly limited, and the conventional type in ink can be used.

Illustratively, the filler (F) may be selected from or include: at least one of nano calcium carbonate, aluminum hydroxide, barium sulfate, silicon dioxide, talcum powder and kaolin.

The content of the component (F) in the radiation-curable composition is 0 to 30%, preferably 0 to 20% by mass of the total amount of the aforementioned components (A) to (E) (when the components D and E are not present, the total amount of the components A to C).

Other Components

In addition to the above components, organic and/or inorganic auxiliaries commonly used in the art may be optionally added to the radiation-curable composition of the present invention, as required by the product application environment, including (but not limited to): leveling agents, dispersing agents, curing agents, surfactants, defoamers, storage stabilizers, and the like, as would be readily determined by one skilled in the art. The total content of the auxiliaries is 0 to 5%, preferably 0 to 3%, in mass percent, of the total amount of the aforementioned components (A) to (E) (when components D and E are not present, the total amount of components A to C).

Optionally, a sensitizer may be added to the system for the purpose of increasing the photosensitivity of the composition, especially when the radiation source is an LED. The sensitizer may be pyrazoline compound, acridine compound, anthracene compound, thioxanthone compound, naphthalene compound, coumarin compound, tertiary amine compound, etc. As the anthracene sensitizer compound, a compound having a structure represented by the following formula (IV) and/or (V):

wherein,

R₈and R₉Each independently represents C₁-C₁₂Alkyl or alkoxy of C₁-C₁₂Aryl or aryloxy of (A), C₃-C₁₂Cycloalkyl of, C₄-C₁₂Is optionally substituted with an alkyl or cycloalkyl alkyl group of (a), optionally,the hydrogens in these groups may each independently be substituted with a halogen, a hydroxy group;

X₁、Y₁、X₂and Y₂Each independently represents hydrogen, alkyl, alkoxy, halogen atom, nitro, sulfonic group, hydroxyl, or amino;

n1 and n2 each independently represent an integer of 0 to 4;

and when n1 and n2 are 2 or more, each X₂And Y₂May be the same as or different from each other.

Illustratively, the anthracene compound may be selected from the following compounds:

the content of the sensitizer in the composition is 0 to 5% by mass, preferably 0 to 2% by mass, of the total amount of the aforementioned components (A) to (E) (when components D and E are not present, that is, the total amount of components A to C).

< preparation and use of radiation-curable composition >

After preparation of the desired pigment dispersion, the above-described compositions of the invention can be prepared by methods conventional in the art of radiation-curable compositions.

Typically, the preparation of the above radiation curable composition comprises the steps of:

(1) preparing a pigment dispersion as described above;

(2) mixing, stirring and dispersing the components (A) - (C) or (A) - (E) and other optional components according to a formula under the conditions of a light-proof or non-active light source (namely, a light source which does not initiate a photocuring reaction, such as a yellow or red safety lamp) and constant pressure and temperature, and filtering (filtering by a filter screen with a specified size to obtain a product with a required particle size).

The fundamental difference of the present invention over the prior art in the preparation of the radiation-curable composition of the present invention is that the pigment dispersion is prepared in advance to obtain a satisfactory pigment dispersion, and then the pigment dispersion is mixed with other components, rather than directly mixing various components such as pigments.

In step (2), the mixing is usually carried out using a mixer, a mill and/or a kneader. Examples of the mixer include a butterfly mixer, a planetary mixer, a tank mixer, a homomixer, or a homodisperser. Examples of the mill include a roll mill, a sand mill, a ball mill, a bead mill, or a line mill. The mixing duration (residence time) is generally from 10 to 120 min.

The radiation curable composition of the present invention is preferably applied by gravure printing or flexography, more preferably by gravure printing, from the viewpoint of cost of the printed layer, production efficiency and decorativeness.

The viscosity (23. + -. 2 ℃ C.) of the composition of the present invention is not particularly limited, and when a coating layer is formed by gravure printing, the viscosity is usually preferably 500 mPas or less, and preferably 10 to 200 mPas. The viscosity of the composition exceeding 200 mPas or lower than 10 mPas may result in "poor coverage", unsatisfactory imparting of decorativeness or unsatisfactory stabilization of the composition during storage. The viscosity of the radiation-curable composition can also be controlled, typically by the use of thickeners or thinners.

The cured coating thickness of the pattern of the radiation-curable composition of the invention may vary depending on the purpose, and is preferably from 0.1 to 20 μm, particularly preferably from 0.5 to 15 μm. A coating layer having a thickness of less than 0.1 μm may not be uniformly formed or may be difficult to print accurately according to design, a coating layer having a thickness of more than 20 μm may consume a large amount of the composition, thereby causing an increase in cost, and uniform application may become difficult, and the coating layer may become brittle and be easily delaminated.

As a coating method of the above radiation-curable composition, there can be also used, without particular limitation, other known methods such as a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, a die coating method, a wire bar coating method and the like.

The radiation-curable composition of the present invention is not particularly limited in the form of the initiation energy source, and the combination of the present invention is irradiated with energy such as ultraviolet light, visible light, infrared light, electron beam, laser, etcExemplary, initiation energy sources include, but are not limited to, ultra-high pressure mercury lamps, medium pressure mercury lamps, mercury xenon lamps, low pressure mercury lamps, metal halide lamps, xenon lamps, deuterium lamps, chemical lamps, LED lamps, fluorescent lamps, tungsten lamps, Nd-YAG3 double wave lasers, He-Cd lasers, nitrogen lasers, Xe-Cl excimer lasers, Xe-F excimer lasers, semiconductor excited solid state lasers, i-rays, h-rays, g-rays, etc., with wavelengths of 200-500nm, electron beam, α -rays, β -rays, gamma-rays, X-rays, and neutron ray energy curing, etc., preferably mercury lamps and UVLED lamps with wavelengths of 200-500nm, irradiation preferably at 50 to 1000mj/cm²The irradiation energy of (1).

The radiation curable composition of the present invention has excellent properties of adhesion fastness, chemical resistance, scratch resistance and the like, and can be typically used for decorative-imparting applications such as an outermost layer disposed as a label and the like. Further, the radiation curable composition of the present invention may be used in plastic labels, and may be used in general in stretch labels, shrink labels, stretch/shrink labels, in-mold labels, adhesive labels, roll labels (labels on roll labels) or heat sensitive adhesive labels. The above-mentioned plastic label has at least a pattern layer formed of the radiation-curable composition of the present invention on one surface of a plastic film, and is preferably disposed as a surface layer, such as the outermost layer or the innermost layer, of the label.

The type of film used in the plastic label of the present invention is selected according to the desired properties, use and cost, such as: at least one of polyester, polyolefin, polystyrene, polyvinyl chloride, polyamide, aramid, polyimide, polyphenylene sulfide, or acrylic resin; preferably one of polyester (polyethylene terephthalate (PET) or poly (ethylene-2-6-naphthalate) (PEN)), polyolefin (one of polypropylene, polyethylene or cycloolefin), polystyrene or polyvinyl chloride.

The film may be a monolayer film or a multilayer film comprising two or more layers arranged according to the desired properties and uses. When the film is a multilayer film, each film may include a film layer composed of a different resin. The film may be any of an unoriented film (unstretched film), a uniaxially oriented film, or a biaxially oriented film, selected depending on the desired properties and use. The heat shrinkage rate (88-92 ℃,10 s) of the above film is not particularly limited, and when the film is used for producing a shrink type plastic label, the heat shrinkage is preferably 3% to 15% in the longitudinal direction, 20% to 80% in the width direction, and the thickness of the film is preferably 10 to 200 μm.

The plastic labels of the present invention are typically applied to containers and used as container labels. Examples of such containers include yogurt cups, milk cups, soft drink bottles, dairy products, juices, wine-based containers, cleaning product containers, or food containers such as sauces, alcoholic beverage bottles, pharmaceutical product containers, can-like containers, and the like, wherein the containers are made of materials including plastics, glass, and metals, and wherein the containers are shaped to include various contoured bottles, containers having a large difference in neck and body diameters, and the like.

Without limitation, the radiation curable composition of the present invention may include the following steps in a particular application:

(1) passing the radiation curable composition through a printing device to form a printed pattern;

(2) cutting the plastic film obtained after the radiation curing into a predetermined width and winding it on a predetermined container with the printed layer facing outward, applying an adhesive in a strip of approximately 2-4mm wide on the side of the end of the plastic film in the longitudinal direction;

(3) the plastic film is wound along a predetermined container so that the aforementioned 2-4mm wide strip is bonded to the end side of another plastic film (hot pressing may also be employed), thereby obtaining a plastic film having a cured film layer conforming to the outer shape of the predetermined container;

(4) the predetermined container marked with the plastic film having the printed layer of the radiation curable composition of the present invention is obtained by shrinking the plastic film into close contact with the container by heat treatment (for example, by a hot air tunnel or a steam tunnel at a predetermined temperature) or infrared heat treatment. Such as: the cylindrical plastic label was attached to a 500 ml PET bottle, and film shrinkage was performed through a steam tunnel at an air temperature of 88 ℃ to obtain a PET film-labeled container having a radiation-curable composition printed layer of the present invention.

Compared with the prior art, the pigment dispersion has good dispersion performance, the radiation curing composition is a solvent-free system, is environment-friendly, has excellent storage stability, can keep the system homogeneous for a long time, has good printing adaptability on various plastic substrates, high curing speed, good adhesiveness of a cured layer, excellent chemical resistance and scratch resistance, and has trackability in the shrinkage process, and printed patterns have the characteristics of neatness, smooth edges, uniform ink color, no obvious odor of products and the like. The radiation curing composition can be printed at high speed, has high production efficiency, is suitable for various plastic film bearing base materials, and is suitable for further popularization and application, and printed products formed on the base materials have good appearance and strong market competitiveness.

Detailed Description

The present invention will be described in further detail with reference to specific examples, which should not be construed as limiting the scope of the present invention.

Examples

Unless otherwise indicated, the starting materials used in the examples are conventional in the art and are commercially available. Unless otherwise indicated, parts in the formula are parts by mass.

The particle size of the pigment dispersion was measured using an Oume Keg TopSizer laser particle size Analyzer.

The viscosity was measured using an NDJ-79A rotational viscometer (Shanghai Changji geology instrument).

The pH value is measured according to the national standard GB/T1717-1986, and specifically comprises the following steps: a10% (m/m) pigment dispersion suspension was prepared in distilled water at 25 ℃ in a glass vessel, the vessel was stoppered with a stopper, vigorously shaken for 1min, allowed to stand for 5min, the stopper was removed, and the pH of the suspension was measured to an accuracy of 0.1 unit.

1. Preparation of pigment dispersions

Pigments, dispersing aids, dispersing monomers were weighed out for use according to the formulations shown in examples 1 to 18 in tables 1,2 and 3.

The dispersing monomers are firstly and uniformly mixed according to the sequence from top to bottom in the table, then the dispersing auxiliary agents are sequentially added into the dispersing monomers according to the sequence from top to bottom in the table, and a homogenizer is used for stirring until the dispersing monomers and the dispersing auxiliary agents are uniformly mixed. The pigment and the dispersion beads were added within 10min, followed by stirring at 2000-3000rpm at a constant temperature of 25 ℃ under normal pressure. When the D90 of the pigment dispersion was 1.5 μm or less as observed by particle size measurement, stirring was stopped and the dispersed beads were filtered off to obtain pigment dispersions 1 to 18.

Wherein the dispersing beads are zirconia ceramic microspheres with the average grain diameter of 0.35 mm; the ratio of the total amount of the pigment dispersoid to the addition amount of the dispersing beads is 1: 1.2.

TABLE 1

In Table 1, pigment Black 1 is MA100 manufactured by Mitsubishi chemical corporation, pigment white 1 is Dupont titanium white R706, and pigment yellow1 is Yuanba

Yellow 3GNP, pigment Red1 is crude gasoline

Red 2020 pigment blue 1 as raw gasoline

Blue 4 GNP.

Other conditions were not changed, and similar technical effects to those of the corresponding examples in table 1 were obtained by using KH550 instead of KH570, or using Solsperse85000 instead of Solsperse 36000. Other conditions are unchanged, and similar technical effects to those of corresponding examples in table 1 can be obtained by replacing I18 with I14, I15 or I19, replacing I3 with I4 or I5, and replacing I6 with I7, I8, I11 or I12.

TABLE 2

In the above table, pigment white 2 is JR-809 of TAYCA CORPORATION, and pigment yellow 2 is raw soda

Yellow 3RLP, pigment Red 2 is raw Ciba Cromophtal RED 2030, pigment Blue 2 is raw Ciba IRGALITE Blue GLO, and pigment Red 3 is raw Ciba

Red A3B, pigment green as raw soda

Green GFNP.

Other conditions were unchanged, and similar technical effects to the corresponding examples in table 2 were obtained using I10 instead of I9, or I20 or I16 instead of I17. Other conditions were unchanged, and similar technical effects to the corresponding examples in table 2 were also obtained using I22, I23, I24, I1 or I2 instead of I21.

TABLE 3

The above pigment dispersions 1 to 18 were all measured to have a pH value in the range of 6 to 8.

The color concentration k of the pigment dispersion is calculated by the formula: pigment amount/(pigment amount + dispersion monomer amount + dispersion aid amount) × 100%, where each amount is a mass part.

In order to reduce the production cost or obtain unexpected better performance (better tensile strength, shear strength, surface tension and the like of a coating film after curing) or fade color concentration and the like, the pigment dispersion can adopt fillers such as barium sulfate, kaolin, calcium carbonate and the like to partially replace (but not completely replace) the addition amount of the pigment, and obtain better using effect.

The viscosity and cumulative particle size distribution number of the pigment dispersions 1-18 were tested and the results are shown in table 4 below. In Table 4, the first viscosity is the initial viscosity of the pigment dispersion, the second viscosity is the viscosity measured after the pigment dispersion is kept at a constant temperature of 80 ℃ for 72 hours and taken out, and has units of mPa. multidot.S, the first D90 is the initial D90 of the pigment dispersion, and the second D90 is the D90 measured after the pigment dispersion is kept at a constant temperature of 80 ℃ for 72 hours and taken out.

TABLE 4

As is clear from Table 4 above, the pigment dispersions 1 to 18 exhibited stable second viscosities after being thermostated at 80 ℃ for 72 hours and also stable second D90 values, and were able to be used in radiation-curable compositions.

2. Formulation of radiation-curable compositions

(1) Examples 19 to 42

① color strength of 50% k was established using the pigment dispersions obtained in examples 1 to 6.

According to the formula shown in Table 5, cationic polymerizable compounds B1 and B2, a cationic photoinitiator C and a sensitizer are respectively and uniformly mixed in advance at the temperature of 20-30 ℃, then raw materials are added into a constant temperature and constant pressure reactor according to the sequence of B1, B2 and C, the sensitizer, a pigment dispersion, a leveling agent BYK307 and a defoamer BYK055, stirred by a stirrer at the rotating speed of 1500-2000rpm under the condition of a yellow light lamp (i.e. a safety lamp which can not trigger reaction), and filtered by a 5 mu m filter screen when the visual inspection mixed liquid is a uniform mixture, so that the radiation curing composition of the invention in the embodiment 19-24 is obtained.

TABLE 5

In the context of Table 5, the following examples are given,

b11 is I47;

b12 is:

b13 is:

b21 is TTA2081 of Jiangsu Tetel;

b22 is TTA26 of Jiangsu Tetel;

b23 is TTA184 of Jiangsu Tetel;

c1 is PAG 20001;

c2 is PAG 30201;

ZGJ1 is

ZGJ2 is

② color strength of 40% k was formulated using the pigment dispersions 7 to 12 obtained in examples 7 to 12.

Radiation curable compositions of examples 25 to 30 of the present invention were obtained according to the formulation shown in Table 6 by referring to the above-mentioned method.

TABLE 6

In the context of Table 6, the following examples are,

b14 is

B15 is

B16 is I54;

b24 is SU-8 bisphenol A type novolac epoxy resin;

c3 is PAG 20002;

ZGJ3 is

The B14, B15 and B16 can be respectively replaced by epoxy 636 or phenyl glycidyl ether XY690, benzyl glycidyl ether XY692, octyl glycidyl ether XY746 or decyl glycidyl ether XY747 in New telechemical industry of Anhui province, and the same using effect can be obtained.

③ color strength of 30% k was prepared in succession using the pigment dispersions obtained in examples 13 to 18.

As shown in Table 7, B1, B2 and C, a radical polymerizable compound D, a radical photoinitiator E and a sensitizer are respectively and uniformly mixed in advance at 20-30 ℃, then raw materials are added into a constant temperature and constant pressure reactor in sequence of B1, B2 and C, D, E, the sensitizer, a pigment dispersion, BYK307 and BYK055, stirred clockwise at the rotating speed of 1500-2000rpm under the condition of a yellow light lamp (i.e. a safety lamp which does not trigger the reaction), when the mixed solution is uniform by visual inspection, the clockwise stirring is stopped, and the uniform mixture is filtered through a 5-micron filter screen, so that the energy curing composition of the invention in the embodiment 31-36 is obtained.

TABLE 7

In the context of Table 7, the following examples are,

b17 is I56;

b18 is

B25 is TTA15 of Jiangsu Tetel;

d1 is Sadoma SR238 HDDA;

d2 is basf LR8986 modified EA;

d3 is Saedoma CN2251PEA,

e1 is Irgacure 184;

e2 is Irgacure 819;

e3 is GencureITX.

④ color strength of 20% k was formulated using pigment dispersion 1/7/11/15/16/17.

Energy curable compositions of examples 37-42 of the present invention were obtained according to the formulation shown in Table 8, with reference to the above-described method.

TABLE 8

In the context of Table 8, the following examples are,

c4 is PAG 30101;

d4 is sartomer SR508 DPGDA;

d5 is basf LR8765 aliphatic EA;

d6 is basf LR8799 PEA;

e4 is Gencure DETX;

e5 is Irgacure 1173;

ZGJ4 is

(2) Comparative example

① comparative example 1

In contrast to example 19 above, which contains pigment dispersion 1.

The preparation method comprises the following steps:

the same starting material as in example 19 was prepared, namely: pigment black 120 parts, Solsperse 360002 parts, I32 parts, I62 parts, TCM 10115 parts, UVR 61102.5 parts, TCM 20912.5 parts, B1114 parts, B1214 parts, B217 parts, C16.5 parts, C22.5 parts, ZGJ 22 parts, BYK 3070.2 parts and BYK 0550.15 parts;

firstly, respectively and independently stirring a dispersion monomer, a dispersion auxiliary agent, a polymeric compound, a photoinitiator and a sensitizer uniformly, then adding the dispersion auxiliary agent into the dispersion monomer, sequentially adding pigment, dispersion beads (the addition amount is half of that of the dispersion beads in example 1), the polymeric compound, the photoinitiator, ZGJ2, BYK307 and BYK055 into a constant-temperature and constant-pressure reactor, and stirring for 5min at a constant speed by using a high-speed stirrer under the condition of a yellow light (namely a safety lamp which can not trigger reaction) to obtain a gelatinous mixture.

② comparative example 2

In contrast to example 25 above, which contained pigment dispersion 7.

The preparation method comprises the following steps:

the same starting material as in example 25 was prepared, namely: 216 parts of pigment white, 91.6 parts of I, 131.6 parts of I, 171.6 parts of I, 20120.8 parts of TCM, 61103.2 parts of UVR, 1417.2 parts of B, 1519 parts of B, 215.5 parts of B, 234.5 parts of B, 16.5 parts of C, 32.5 parts of C, 11 parts of ZGJ, 32 parts of ZGJ, 3070.2 parts of BYK and 0550.15 parts of BYK;

firstly, dispersing monomers, a dispersing auxiliary agent, a polymeric compound, a photoinitiator and a sensitizer are respectively and independently stirred uniformly, then the dispersing auxiliary agent is added into the dispersing monomers, then pigment, dispersing beads (the addition amount is 0.4 times of that of the dispersing beads in example 7), the polymeric compound, the photoinitiator, the sensitizer, BYK307 and BYK055 are sequentially added into a constant-temperature and constant-pressure reactor, and a gelatinous mixture is obtained when the mixture is stirred at a constant speed for 4min by using a high-speed stirrer under the condition of a yellow light (i.e. a safety light which can not trigger reaction).

③ comparative example 3

In contrast to example 35, which contains pigment dispersion 17, described above.

The preparation method comprises the following steps:

the same starting material as in example 35 was prepared, namely: pigment blue 110.5 parts, I321.05 parts, I351.05 parts, I381.2 parts, UVR 61007.5 parts, UVR 61107.5 parts, I544.5 parts, B1717 parts, B1211 parts, B244.5 parts, B257.5 parts, C12 parts, C34 parts, D211.7 parts, D17 parts, E11 parts, E20.5 parts, E30.5 parts, ZGJ 13 parts, ZGJ 21 parts, BYK 3070.2 parts and BYK 0550.15 parts;

firstly, a dispersing monomer, a dispersing auxiliary agent, a B1/B2 polymeric compound, a photoinitiator C, a free radical polymeric compound D, a photoinitiator E and a sensitizer are respectively and independently stirred uniformly, then the dispersing auxiliary agent is added into the dispersing monomer, and then a pigment, a dispersing bead (the addition amount is 0.3 times of that of the dispersing bead in the example 17), a B1/B2 polymeric compound, the photoinitiator C, the free radical polymeric compound D, the photoinitiator E, the sensitizer, BYK307 and BYK055 are sequentially added into a constant temperature and constant pressure reactor, and when the mixture is stirred at a constant speed for 8 hours by using a high-speed stirrer under the condition of a yellow light lamp (namely a safety lamp which can not trigger the reaction), a uniform mixture determined by the testing method cannot be obtained.

As can be seen from the above comparative examples, there is a risk that a gelatinous mixture or a non-homogeneous mixture is obtained with the solution of the comparative example, so that the pH or D90 cannot be tested, nor can it be further equated with the radiation-curable composition of the present invention and the advantageous effects of the present invention be obtained. The gelatinous mixture or the heterogeneous mixture can only be treated as waste at the later stage, and the scheme as shown in a comparative example is easy to cause the problems of reducing the production efficiency, increasing the production cost, increasing the environmental pollution pressure and the like.

3. Performance testing and evaluation of radiation-curable compositions

The performance test and evaluation are carried out on the samples of the examples according to QBT 1046-:

(1) storage stability test

The inks of examples 19 to 42 were all measured to have a viscosity of 150mPa.S or less.

The storage stability of the inks to be tested is determined with reference to the method for testing the storage stability of GB-T6753.3-1986. The specific method comprises the following steps: covering a cover on two cans of samples which are filled with the same ink and have the same weight, then placing the two cans of samples in a constant-temperature drying oven at 80 ℃, taking out the samples after 48 hours, placing the samples at room temperature for 24 hours, then measuring the viscosity of the ink to obtain the post viscosity, and carrying out grading evaluation according to the ratio percentage of the post viscosity to the initial viscosity (the ratio percentage of the two cans of samples which are the same is close to or the same and is in the following division range, otherwise, the ratio percentage is not considered), wherein the specific values are as follows:

○, the viscosity change ratio is below 5%;

◎, the viscosity change proportion is more than 5 percent and less than 10 percent;

●: the viscosity change ratio is more than 10%.

As a result of the test, the storage stability test results of examples 19 to 42 were all ○, i.e., the viscosity change ratio was 5% or less.

(2) Cure drying Rate test

The ink to be tested is printed by using a Sonde solvent-free gravure printing machine (model: A380), and an LED lamp is additionally arranged on the machine to be used as a radiation light source. The ink to be tested is transferred to a PETG film (provided by Guangdong Hua packaging material Co., Ltd.) by a gravure printing machine, the printing thickness is set to be 5 mu m, and the irradiation intensity of an LED light source is 20w/cm²。

After the light irradiation is finished, the coating is placed for 24h, and the surface curing condition is evaluated by referring to a finger touch method in a paint film drying time test standard GB/T1728-1979, namely, the coating is lightly touched by fingers to confirm the surface drying by smooth surface, no hand sticking and no finger mark pressing. The drying speed is expressed in units of m/min as the maximum line speed to achieve surface drying effect.

The test method is adopted in the embodiments 19-24, and the LED lamp with the wavelength of 365nm is additionally arranged on the machine to be used as a radiation light source; examples 25-30 the above test method was used with an LED lamp having a wavelength of 385nm added to the machine as the radiation source; examples 31-36 adopt the above-mentioned test method, set up the LED lamp with 395nm of wavelength as the radiation light source on the machine; in examples 37 to 42, the above test method was used, and an LED lamp having a wavelength of 405nm was added to the machine as a radiation source; the results are shown in Table 9.

TABLE 9

Example 19	Example 20	Example 21	Example 22	Example 23	Example 24
						Drying speed	245	250	240	260	260	255
Example 25	Example 26	Example 27	Example 28	Example 29	Example 30
						Drying speed	235	240	245	245	250	240
Example 31	Example 32	Example 33	Example 34	Example 35	Example 36
						Drying speed	235	230	240	240	230	230
Example 37	Example 38	Example 39	Example 40	Example 41	Example 42
						Drying speed	235	240	250	245	240	240

The curing and drying speed test results show that the curing and drying speeds of the compositions of different examples are different under the same illumination condition. In the research and development process, the applicant finds that the curing and drying speeds of different examples can be tested at the same speed by properly adjusting the formula of the examples (such as increasing the addition amount of the photoinitiator) and then testing under the same illumination condition; in addition, the formula of the above examples is kept unchanged, and the test results with the same curing and drying speed of different examples can be obtained by setting different illumination conditions for each example.

4. Test and evaluation of print Performance

The linear speed of the ink of the example on the gravure printing machine was set at 230m/min, a PET film (YMR 286H PETG heat shrinkable film provided by Henan Yinjada new material) was used as a base material, the printing thickness was set at 5 μm, and the irradiation intensity of the LED light source was 18w/cm²365nm LED lamps were used as radiation light sources in examples 19 to 24, 385nm LED lamps were used as radiation light sources in examples 25 to 30, 395nm LED lamps were used as radiation light sources in examples 31 to 36, and 405nm LED lamps were used as radiation light sources in examples 37 to 42, and the cured coating was left for 24 hours after exposure to light, and the cured coating adhesion fastness, print appearance, odor residue, and the like were evaluated.

(1) Test for adhesion fastness

Referring to the GB/T13217.7-2009 liquid ink adhesion test method, under the conditions of 25 +/-1 ℃ and humidity of 65% +/-5%, a tape meeting the standard GB 7707 is adhered to an ink printing surface, the tape is rolled back and forth 3 times on a tape press, the tape is placed for 5min, a sample is clamped on an A disc, the tape with an exposed head is fixed on a B disc, then the A disc is started, the tape is opened at the speed of 0.6-1.0m/s in a rotating way, the uncovered part is covered by a semitransparent millimeter paper with the width of 20mm, the number of grids of an ink layer and the number of the uncovered ink layer are counted respectively, and the A (%) is calculated as [ A1/(A1+ A2) ] multiplied by 100%, wherein A represents the ink adhesion, A1 represents the number of the ink layer, A2 represents the number of the uncovered ink layer, and the A ≧ 90 is understood as meeting the performance index ("○"), 80 < 90 is understood as being slightly worse but △ is understood as being equal to be equal to the poor adhesion (× 80).

The results of the adhesion fastness tests for the above examples 19-42 of the present invention were all "○".

(2) Evaluation of appearance of printed article

According to the GB/T7707-2008 intaglio decoration printed matter standard, intaglio printing with the depth of 10-18 mu m is adopted, the printed matter after being placed for 24 hours is placed under an observation light source which accords with CY/T3 regulations, and is identified through visual inspection, the printed matter is neat and clean, no obvious ink stain, residue and knife thread exist, characters are printed clearly and completely, no residue and deformation exist, the characters smaller than 7.5P do not influence reading, the edges of the printed marks are smooth, the ink color is uniform, no obvious water texture exists, the printing level is transited stably, no obvious gradation jump exists, the screen points are clear and uniform, no obvious deformation and residue exist, the printing color accords with the requirement of paying a print sheet, namely, the printed matter is qualified (' ○ '), and if any one is not ideal, the printed matter is marked as unqualified (× ').

The results of the test for the appearance evaluation of the prints of examples 19 to 42 of the present invention were all "○".

(3) Odor residual test

The products cured in the examples 19 to 42 are put into a sealed bag, sealed and placed for 24 hours at room temperature, and then the bag opening is opened for judgment by artificial olfaction. The evaluation grades were as follows:

○ no obvious odor;

x: pungent odor.

The results of the odor residual tests for examples 19-42 of the present invention were all "○".

(4) Chemical resistance

After fifty times of back and forth movement (once for each time) of a cotton swab impregnated with methyl ethyl ketone on the sample containing the cured layer, the surface of the printed surface was visually observed after the methyl ethyl ketone had evaporated.

Samples with non-peeled print side were considered to have good chemical resistance ("○"), samples with partially peeled print side (< 50% area) were considered to have general chemical resistance ("△"), and samples with large peeled print side (. gtoreq.50% area) were considered to have poor chemical resistance ("x").

The chemical resistance test results for inventive examples 19-42 were all "○".

(5) Resistance to wrinkles

From the prepared solidified layer-containing samples, 100mm long and 100mm wide samples were sampled. The samples were held between both ends by hand and rubbed ten times by hand, and then the area of the residual resin layer on the surface of the wrinkled test piece was visually observed to evaluate the wrinkle resistance.

Samples with a residual area of 90% or more were evaluated as having good crease resistance ("○"), and samples with a residual area of less than 90% were evaluated as having poor crease resistance ("x").

The results of the crease resistance tests for inventive examples 19-42 were all "○" as tested.

(6) Scratch resistance

Using a scratch resistance test apparatus supplied by Electron from Dongguan, samples 100mm long and 100mm wide were sampled from the plastic labels prepared in examples 19 to 42, the samples were fixed by placing on a flat plate, the printed surface was moved in a straight line with the end of a conical pin loaded with 500g weight on the upper part thereof, and scratches on the surface of the printed surface were observed.

The evaluation was made according to the following criteria:

good scratch resistance ("○");

partial delamination of the coating, somewhat poor, but usable scratch resistance ("△");

obviously stripping the coating: scratch resistance was poor (x).

The results of the scratch resistance tests for inventive examples 19-42 were all "○".

(7) Heat shrinkage test

Samples 100mm long and 100mm wide were sampled from the plastic substrates containing the printing ink layers prepared in examples 19 to 42, and the printing ink layers were observed after passing the samples through a hot air tunnel at a temperature of 90 ℃.

The evaluation grades were as follows:

○, the printing layer is deformed by thermal contraction following the substrate film;

x: the printed layer does not follow the thermal shrinkage deformation, detachment or breakage of the base film.

The heat shrinkage test results for the inventive example samples were all "○".

In the above test experiments, the applicant replaced the LED lamp with a UV mercury lamp (wetting RW-UVAP202-20gl, wavelength range 200-450 nm), and set the sensitizer addition amount in the formulations of examples 19-42 to 0, and the examples of the present invention were tested to achieve or be superior to the above technical effects under the same light intensity or less.

From the test results, the radiation curing composition has good performances in the aspects of adhesion fastness, appearance of printed products, odor property, chemical resistance, wrinkle resistance, scratch resistance, heat shrinkage and the like, is suitable for shallow screen printing, can effectively avoid the problems of losing points of printed shallow screens, color deviation of printed products, fuzzy image-text layering sense and difficulty in finishing high-precision and high-quality printed patterns in the existing shallow screen printing technology, and is suitable for further popularization and application on the surfaces of composite films for food packaging, vacuum packaging films for food packaging, beverage containers (special-shaped bottles/long-neck bottles outer labels, sealing labels) and the like.

5. Further Performance testing and evaluation

The radiation curing composition of the invention is respectively applied to other film substrates under the condition of gravure process, and the application performance of the radiation curing composition is further verified.

For the above-mentioned examples 19 to 42, the line speed on the gravure printing machine was set to 220m/min, the heat shrinkable film FR608, PP film (BOPP film provided by Guangdong Hua industries, Ltd.) and PS film (BOPS film provided by Guangdong Hua industries, Ltd.) provided by the high dimensional film were used as the base materials, the thickness of the printed film was set to 5 μm, and the light source irradiation intensities were all 18W/cm²。

Examples 19 to 24 used 365nm wavelength LED lamps as radiation sources, examples 25 to 30 used 385nm wavelength LED lamps as radiation sources, examples 31 to 36 used 395nm wavelength LED lamps as radiation sources, examples 37 to 42 used 405nm wavelength LED lamps as radiation sources, and after exposure, they were left to stand for 24 hours.

The cured coatings were evaluated using the adhesion test method described previously.

The results showed that the evaluation results of examples 19 to 42 were all "○" when the heat shrinkable film FR608, PP film and PS film were used as substrates.

From the above test results, the radiation curable composition of the present invention can be further popularized and applied on the surface of the substrate such as the FR608 heat shrinkable film, PP film, PS film, etc.

As can be seen from the above evaluation results and embodiments, the radiation curable composition of the present invention has the characteristics of high storage stability, fast curing speed, good adhesion of the cured layer, neat pattern of the printed matter, smooth edge, uniform ink color, no noticeable odor of the product, etc., can be well applied to plastic films by gravure printing or flexographic printing, can be cured rapidly, is useful for efficient production of plastic labels, can satisfactorily adhere to plastic films, and the cured layer can satisfactorily follow the deformation of the base film during shrinkage and is excellent in chemical resistance, scratch resistance, wrinkle resistance, etc. Therefore, the radiation curing composition is suitable for being used as a plastic label, is particularly suitable for plastic labels of glass bottles and plastic containers such as PET (polyethylene terephthalate) bottles and metal containers, and is suitable for further large-scale popularization and application.

Claims

1. A pigment dispersion comprising a pigment, a dispersing aid and a dispersing monomer, wherein the dispersing aid is selected from or comprises a silicon-containing compound.

2. The pigment dispersion according to claim 1, wherein the dispersing aid is selected from or comprises at least one of: KH570, KH560, KH550, A-151, A-132, Solsperse 24000, Solsperse 28000, Solsperse32000, Solsperse36000, Solsperse85000, Solsperse 86000.

3. The pigment dispersion according to claim 1, characterized in that: the dispersing aid is selected from or comprises a silicon-containing epoxy compound, and the silicon-containing epoxy compound has a structure shown in the following structural general formula (I):

wherein,

R₀₁each independently is an oxetanyl or oxiranyl group which is

The group containing the ethylene oxide group is ethylene oxide alkoxy;

p is an integer from 1 to 3, q is an integer from 1 to 3, and p + q is 4;

R₀₃is represented by C₁-C₁₀Straight or branched alkyl of (2), C₂-C₃₀Alkenyl of (a), and R₀₃In (C-CH)₂Optionally substituted by-O-, -COO-, -OCO-or

R₀₄is methyl or ethyl;

4. The pigment dispersion according to claim 1, characterized in that: the dispersing aid is selected from or comprises at least one of fluorine-containing silicon-containing epoxy compounds.

5. The pigment dispersion according to claim 1, characterized in that: the dispersing monomer is selected from or comprises a compound of the general structural formula (I) in claim 3, with the proviso that R₀₂Is C₁-C₅Linear or branched alkyl.

6. The pigment dispersion according to any one of claims 1 to 5, characterized in that: the addition amounts of the pigment and the dispersing monomer are 30 to 50 parts and 50 to 70 parts, respectively, based on 100 parts by mass of the total amount of the pigment and the dispersing monomer, and the addition amount of a single dispersing aid is 0.1 to 0.3 times the addition amount of the pigment.

7. The pigment dispersion according to claim 1, characterized in that: the D90 of the pigment dispersion was 0.8 to 2 μm.

8. The pigment dispersion according to claim 7, characterized in that: the D90 of the pigment dispersion was 0.8 to 1.8. mu.m.

9. The pigment dispersion according to claim 8, characterized in that: the D90 of the pigment dispersion was 0.8 to 1.5. mu.m.

10. The pigment dispersion according to claim 1, characterized in that: the pH of the pigment dispersion is 4-10.

11. The pigment dispersion according to claim 10, characterized in that: the pH of the pigment dispersion is 5-10.

12. The pigment dispersion according to claim 11, characterized in that: the pH of the pigment dispersion is 5.5 to 9.5.

13. A method of preparing the pigment dispersion of any one of claims 1 to 12, comprising the steps of:

14. Use of the pigment dispersion according to any one of claims 1 to 12 in a solvent-free composition.

15. Use according to claim 14, characterized in that: the composition is an ink for flexographic, letterpress, gravure, screen, thermal transfer, lithographic, digital or ink jet printing.

16. A radiation-curable composition comprising: the pigment dispersion (A) according to any one of claims 1 to 12, a cationically polymerizable compound (B) and a cationic photoinitiator (C).

17. The radiation-curable composition according to claim 16, wherein the cationically polymerizable compound (B) is selected from or comprises: oxetane compounds, epoxy compounds and vinyl ether compounds.

18. The radiation-curable composition of claim 16, wherein: the cationically polymerizable compound (B) is used in combination with an oxetane compound (B1) and an epoxy compound (B2).

19. The radiation-curable composition of claim 16, wherein: the cationic photoinitiator (C) is one or a combination of two or more selected from iodonium salt, sulfonium salt and aryl ferrocenium salt.

20. The radiation-curable composition of claim 16, wherein: further comprising a radical polymerizable compound (D) and a radical photoinitiator (E).

21. The radiation-curable composition according to any one of claims 16 to 20, characterized in that: it also contains sensitizer.

22. The radiation-curable composition of claim 21, wherein: the sensitizer is an anthracene sensitizer compound and has a structure shown in the following formula (IV) and/or (V):

wherein,

R₈and R₉Each independently represents C₁-C₁₂Alkyl or alkoxy of C₁-C₁₂Aryl or aryloxy of (A), C₃-C₁₂Cycloalkyl of, C₄-C₁₂Optionally, the hydrogens in these groups may each be independently substituted with halogen, hydroxy;

n1 and n2 each independently represent an integer of 0 to 4;

23. Preparation of the radiation-curable composition according to any one of claims 16 to 22, comprising the steps of:

(1) preparing a pigment dispersion according to claim 13;

(2) the components (A) - (C) or (A) - (E) and other optional components are mixed, stirred and dispersed under the conditions of light protection or inactive light source, constant pressure and constant temperature, and then filtered.

24. Use of the radiation curable composition of any one of claims 16 to 22 in gravure printing or flexographic printing.

25. Use of the radiation curable composition of any one of claims 16 to 22 in a plastic label.