GB2256874A - Photocurable compositions - Google Patents
Photocurable compositions Download PDFInfo
- Publication number
- GB2256874A GB2256874A GB9112334A GB9112334A GB2256874A GB 2256874 A GB2256874 A GB 2256874A GB 9112334 A GB9112334 A GB 9112334A GB 9112334 A GB9112334 A GB 9112334A GB 2256874 A GB2256874 A GB 2256874A
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- water
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- 239000000203 mixture Substances 0.000 title claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 229920002635 polyurethane Polymers 0.000 claims abstract description 13
- 239000004814 polyurethane Substances 0.000 claims abstract description 13
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003086 colorant Substances 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- 239000012949 free radical photoinitiator Substances 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 4
- 239000008399 tap water Substances 0.000 claims description 3
- 235000020679 tap water Nutrition 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 7
- 238000007650 screen-printing Methods 0.000 abstract description 4
- 239000004922 lacquer Substances 0.000 abstract description 2
- 239000002966 varnish Substances 0.000 abstract description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 abstract 1
- 239000000049 pigment Substances 0.000 description 13
- 239000000976 ink Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 5
- -1 aromatic isocyanate Chemical class 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229960000834 vinyl ether Drugs 0.000 description 4
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- WVXLLHWEQSZBLW-UHFFFAOYSA-N 2-(4-acetyl-2-methoxyphenoxy)acetic acid Chemical compound COC1=CC(C(C)=O)=CC=C1OCC(O)=O WVXLLHWEQSZBLW-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 description 2
- 150000004072 triols Chemical class 0.000 description 2
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- FOWNZLLMQHBVQT-UHFFFAOYSA-N 1-ethenoxy-2-[2-(2-ethenoxypropoxy)propoxy]propane Chemical compound C=COCC(C)OCC(C)OCC(C)OC=C FOWNZLLMQHBVQT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 240000000254 Agrostemma githago Species 0.000 description 1
- 235000009899 Agrostemma githago Nutrition 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000007376 cm-medium Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- KCWDJXPPZHMEIK-UHFFFAOYSA-N isocyanic acid;toluene Chemical compound N=C=O.N=C=O.CC1=CC=CC=C1 KCWDJXPPZHMEIK-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Photocurable compositions include a photopolymerisable binder comprising a water reducible multi-functional polyurethane acrylate oligomer, a multi-functional acrylate monomer, water, and a vinyl ether monomer, and a free radical photoinitiator. They show properties exhibited by similar compositions containing N-vinyl-2-pyrrolidone without containing it, and can be used to produce prints on paper and paper related products without the release of harmful solvents or monomers. The composition may be in the form of a varnish or lacquer, or may include a colorant and be in the form of an ink, e.g. for screen printing.
Description
PHOTOCURABLE COMPOSITIONS
This invention concerns photocurable compositions, for example for producing prints and printed display graphics on paper and paper related products, e.g. card and corrugated card.
Examples of hitherto proposed compositions for such end uses include: - (i) Cellulosic polymers and a co-resin, e.g. a rosin modified phenolic dispersed in an aromatic hydrocarbon solvent, flow control agents and colorants being present.
Compositions of this type typically have a solids content of 35 to 50 percent by weight and they dry by evaporation of the solvent.
(ii) Alkali susceptible acrylic resins dispersed in water with a coalescing agent, neutralizing agents and flow agents.
Drying is effected by the action of -heat evaporating the water and causing the composition to coalesce. The solids content of these compositions is typically 25 to 60 percent by weight.
(iii) Epoxy acrylate polymers and/or polyurethane acrylate oligomers dispersed in mono- and/or multi-functional acrylate monomers with a free radical initiator. Again, flow agents and colorants would be present. Curing is effected by exposure of the compositions to ultraviolet light. The curable materials represent 100 percent of these compositions.
Coatings of compositions of type (i) in the form of inks can be dried quickly and give good color depth and cleanliness of tone. However, the solvent in the compositions can cause press stability problems as a result of solvent evaporation from the ink on the printing press. Furthermore, the solvent which must be evaporated to effect full drying can pose environmental problems.
Compositions of type (ii), although potentially environmentally safer than compositions of type (i), can give rise to problems in use, the high water content (25 to 60 percent), leading to the substrate to which they are applied being affected causing curling and cockle. When producing multiple prints by repeated printing on the same substrate over previous printing, rewetting of the earlier prints takes place, which can be disadvantageous.
Coatings of compositions of type (iii) can be cured very rapidly, but the cured coatings tend to be very glossy with a high build due to the 100 percent content of polymerizables.
This can be a particular problem when multiple printing is effected, leading to the print having poor 'feel'.
More recently it has been proposed to combine the high speed curing which can be effected with free radically curable compositions with the greater environmental safety of water-containing compositions, to achieve free radically curable compositions which can be reduced in viscosity by the addition of water. Water in the compositions is removed during the ultra-violet curing operation, leading to rapidly curable coatings which have a low feel, due to the lower overall solids content of about 65 percent, without the problems encountered with compositions of type (ii). A typical composition of this type would consist of a water-tolerant epoxy acrylate and/or a polyurethane acrylate dispersed in multi-functional acrylate monomers with a free radical initiator, water being present in an amount of from 25 to 40 percent by weight of the composition.Flow agents and colorants would also be present.
Compositions of this type generally benefit from the addition of a vinyl-pyrollidone derivative, e.g. N-vinyl-2pyrollidone, these derivatives having an excellent viscosity reducing action, only small quantities being required to achieve a high degree of viscosity reduction. This is unlike the effect of other acrylate monomers or indeed water.
More recently, compositions containing vinyl-pyrollidone derivatives have come under scrutiny on health and safety grounds, and their use in commercial compositions, for example in the screen printing industry, is becoming less desirable.
Although mono-functional and/or multi-functional acrylate monomers may be used in place of N-vinyl-2-pyrollidone, the viscosity reducing action of most is inferior to that of
N-vinyl-2-pyrollidone.
It has been proposed to use vinyl ethers in ultra-violet initiated, cationically curable compositions, these ethers having some properties in common with N-vinyl-2-pyrollidone, e.g. viscosity reduction, although they are thought not to take part readily in free radical initiated reactions.
According to the present invention there is provided a photocurable composition comprising: photocurable composition comprising: (a) a photopolymerisable binder comprising a water reducible multi-functional polyurethane acrylate oligomer, a multi-functional acrylate monomer, water, and a vinyl ether monomer; and (b) a free radical photoinitiator.
Surprisingly, compositions of the present invention have exhibited similar desirable properties to those containing
N-vinyl-2- pyrollidone but without containing it.
The multi-, e.g. di- or tri-, functional polyurethane acrylate oligomers should be water reducible, i.e. be dilutable with water. They are preferably liquid or semi-solid at ambient temperature. They can be formed by known methods, for example by reacting an aromatic isocyanate, e.g. toluene di-isocyanate, with 2-hydroxyethyl acrylate. Prior to acrylation of the isocyanate, it can, if desired, be extended to modify the properties of the oligomer obtained after acrylation. Compositions of the present invention preferably contain from 20 to 60 percent by weight of a multi-functional polyurethane acrylate oligomer.
The multi-, e.g. di-, tri- or tetra-, functional acrylate monomer usually serves to increase the crosslink density of the compositions, and thus impart a harder cured film surface. Examples of such monomers include alkyleneoxy diacrylates, e.g. triethylene glycol diacrylate, tripropylene glycol diacrylate; propoxylated neo-pentyl glycol diacrylate; and acrylates of triols and alkoxy extended triols, e.g.
trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated trimethylolpropane triacrylate. The multi-functional acrylate monomer is preferably present in an amount of from 8 to 35 percent by weight of the composition.
The vinyl ether is preferably present in an amount of from 2 to 30 percent by weight based on the composition. Typically the vinyl ether will have a boiling point of from 100 to 200"C. Examples of vinyl ethers which can be used include 1,4-cyclohexane dimethanol divinyl ether, hydroxybutyl vinyl ether, triethylene glycol divinyl ether, hydroxybutyl vinyl ether iso-phthalate and 1,4-cyclohexane dimethanol divinyl ether glutarate ester.
The photoinitator should be capable of producing free radicals upon irradiation by ultra-violet light. Any of a wide variety of photoinitiators can be used, mixtures of liquid aryl ketones being preferred. The amount of photoinitiator used will usually be from 2 to 10 percent based on the total photopolymerisable materials in the compositions. Some latitude is generally allowed to compensate for pigment blocking effects.
Water preferably represents from 10 to 50 percent by weight of compositions of the present invention. It can be common tap water, but it is more preferably deionised water, calcium ions for example having been replaced by hydrogen ions or a solubilising metal ion by a single passage of tap water over an ion-exchange resin, e.g. Amberlite (Trade Mark). However, the degree of hardness of the water has not been found to be a critical factor.
Compositions of the present invention can be in the form of a photocurable varnish or lacquer. However, they preferably include a colorant, for example a pigment, either as a dry powder or as a pigment dispersion, and a surfactant. When used as a dispersion, e.g. in ethylene glycol, the pigment preferably represents about 50 percent of the dispersion.
When present as a dry pigment the colorant preferably forms from 1 to 30 percent by weight of the compositions.
Pigmented compositions of the present invention are advantageously in the form of inks, for example for screen printing.
Other materials which can be present in compositions of the present invention include flow controllers, for example polyacrylates (e.g. Modaflow - ex Monsanto); silicone fluids, for example as 100 percent solutions of poly-(methyl siloxanes) (e.g. Flll/100); and materials known for modifying the surface properties of such compositions, for example polyethylene or polypropylene waxes (e.g. Polymist B-6 - ex
Allied Chemicals), typically in the amounts used hitherto.
Compositions of the present invention will generally be used and cured by applying them to a substrate and thereafter exposing them to a source of ultra-violet radiation to cure and harden them.
The present invention therefore further provides a method of producing a cured coating on a substrate, the method comprising applying a composition according to the invention to a substrate and thereafter exposing the composition to ultra-violet light to effect free radical curing of the composition. The substrate can be of paper, card or a corrugated/fluted card.
Compositions of the present invention have been of particular value in forming screen printed decorations on flat paper/cardboard substrates for graphic arts and display, without the release of harmful solvents or monomers, whilst retaining desirable properties normally associated with formulations containing N-vinyl-2-pyrollidone or a solvent.
The following Examples are given by way of illustration only.
All parts are percentages by weight of the total composition unless stated otherwise. A tri-functional water reducible polyurethane acrylate used in each of the Examples.
Example 1
An ink was prepared by mixing the following ingredients, followed by roll grinding:water reducible polyurethane acrylate oligomer 35 parts water 35 parts ethoxylated trimethylol propane triacrylate 8 parts photoinitiator 5 parts 1,4-cyclohecane dimethanol-divinyl ether 8 parts levelling agent (Flll/100) 2 parts wax (Polymist B12) 0.5 part pigment (e.g. Pigment Red 2) 6.5 parts
This ink was printed by screen printing techniques on to a medium weight art paper using a polyurethane squeegee and a semi-automatic Svecia flat bed printer with a 150 mesh screen. The print so produced was cured by exposure to 2 150 mj/cm of ultra-violet light from a pair of 80W/cm medium pressure mercury vapor lamps having a spectral output predominantly at a wavelength of 284 and 365 nm. The cured print was assessed for water resistance, gloss, curl, rub/scuff and feel.
The results of these tests are given in the accompanying
Table.
Example 2
An ink was prepared as described in Example 1 by mixing and roll grinding the following ingredients:water reducible polyurethane acrylate oligomer 35 parts water 35 parts ethoxylated trimethylol propane triacrylate 8 parts photoinitiator 5 parts tripropylene glycol divinyl ether 8 parts levelling agent (Flll/100) 2 parts wax (Polymist B12) 0.5 part pigment (e.g. Pigment Red 2) 6.5 parts
This ink was printed and tested as described in Example 1, the results being given in the accompanying Table.
Example 3
An ink was prepared as described in Example 1 by mixing and roll grinding the following ingredients:water reducible polyurethane acrylate 35 parts water 35 parts ethoxylated trimethylol propane triacrylate 8 parts photoini tiator 5 parts hydroxybutyl vinyl ether 8 parts levelling agent (Flll/100) 2 parts wax (Polymist B12) 0.5 part pigment (e.g. Pigment Red 2) 6.5 parts
This ink was printed and tested as described in Example 1, the results being given in the accompanying Table.
Example 4 (comparison)
An ink was prepared as described in Example 1 by mixing and roll grinding the following ingredients:water reducible polyurethane acrylate 35 parts water 35 parts ethoxylated trimethylol propane triacrylate 8 parts photoinitiator 5 parts
N-vinyl-2-pyrollidone 8 parts levelling agent (Flll/100) 2 parts wax (Polymist B12) 0.5 part pigment (e.g. Pigment Red 2) 6.5 parts
This ink was printed and tested as described in Example 1, the results being given in the accompanying Table.
Table
Example Water resistance Gloss Curl Rub/Scuff Feel
1 4 5 4 5 5
2 5 4 4 5 5
3 5 5 5 5 4
4 5 5 4 5 5
The compositions of Examples 1, 2 and 3 were substantially equivalent to or indeed even superior to that of Example 4 which contained N-vinyl-2-pyrollidone.
Claims (11)
1. A photocurable composition comprising: (a) a photopolymerisable binder comprising a water reducible multi-functional polyurethane acrylate oligomer, a multi-functional acrylate monomer, water, and a vinyl ether monomer; and (b) a free radical photoinitiator.
2. A composition according to claim 1, wherein the photopolymerisable binder represents from 20 to 60 percent by weight of the composition.
3 A composition according to claim 1 or claim 2, wherein the water is tap water or deionised water.
4. A composition according to any of the preceding claims, wherein the water represents from 10 to 50 percent by weight of the composition.
5. A composition according to any of the preceding claims, wherein the vinyl ether has a boiling point of from 110 to 200"C.
6. A composition according to any of the preceding claims, wherein the vinyl ether represents from 2 to 30 percent by weight of the composition.
7. A composition according to any of the preceding claims, including a colorant.
8. A composition according to claim 7, wherein the colorant represents from 1 to 30 percent by weight of the composition.
9. A composition according to any of the preceding claims, in the form of an ink.
10. A method of producing a cured coating on a substrate, the method comprising applying a composition according to any of the preceding claims to a substrate and thereafter exposing the composition to ultra-violet light to effect free radical curing of the composition.
11. A method according to claim 10, wherein the substrate comprises paper, card or a cdrrugated/fluted card.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9112334A GB2256874B (en) | 1991-06-07 | 1991-06-07 | Photocurable compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9112334A GB2256874B (en) | 1991-06-07 | 1991-06-07 | Photocurable compositions |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9112334D0 GB9112334D0 (en) | 1991-07-24 |
| GB2256874A true GB2256874A (en) | 1992-12-23 |
| GB2256874B GB2256874B (en) | 1994-12-14 |
Family
ID=10696310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9112334A Expired - Fee Related GB2256874B (en) | 1991-06-07 | 1991-06-07 | Photocurable compositions |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2256874B (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2305183A (en) * | 1995-09-18 | 1997-04-02 | Lisco Inc | UV curable ink for game ball and method of printing |
| GB2311787A (en) * | 1996-04-02 | 1997-10-08 | Sericol Ltd | Printing Ink |
| GB2314851A (en) * | 1996-07-02 | 1998-01-14 | Sericol Ltd | A jet ink |
| WO1998032780A1 (en) * | 1997-01-23 | 1998-07-30 | Dsm N.V. | Liquid curable resin composition |
| EP0756609A4 (en) * | 1994-04-19 | 1998-12-02 | Univ Lehigh | PRINTING INK COMPOSITIONS, METHODS OF MAKING AND USES THEREOF |
| US5854300A (en) * | 1996-04-02 | 1998-12-29 | Sericol Limited | Printing ink |
| EP0849728A3 (en) * | 1996-12-20 | 1999-01-07 | Mitsui Chemicals, Inc. | Optical recording medium |
| WO1999007796A1 (en) * | 1997-08-05 | 1999-02-18 | Sericol Limited | An ink jet ink |
| US6013330A (en) * | 1997-02-27 | 2000-01-11 | Acushnet Company | Process of forming a print |
| EP0997508A1 (en) * | 1998-10-29 | 2000-05-03 | Agfa-Gevaert naamloze vennootschap | New ink compositions for ink jet printing |
| US6149983A (en) * | 1995-09-18 | 2000-11-21 | Spalding Sports Worldwide, Inc. | UV curable ink containing aluminum trihydroxide |
| US6248804B1 (en) | 1997-02-27 | 2001-06-19 | Acushnet Company | Ultraviolet and or/ visible light curable inks with photoinitiators for game balls, golf balls and the like |
| GB2357514A (en) * | 1999-12-23 | 2001-06-27 | Sericol Ltd | An ink for decoration of paper substrates for poster displays |
| US6310115B1 (en) | 1998-10-29 | 2001-10-30 | Agfa-Gevaert | Ink compositions for ink jet printing |
| EP1164149A1 (en) * | 2000-06-15 | 2001-12-19 | Tarkett Sommer S.A. | Compositions based on emulgated UV-crosslinkable resins and their application as varnish layer for floor and wall coatings |
| GB2371551A (en) * | 2001-01-29 | 2002-07-31 | Sericol Ltd | A Printing Ink |
| US6428862B1 (en) | 1998-04-28 | 2002-08-06 | Canon Kabushiki Kaisha | Ink, ink-jet recording method using the same, and photopolymerization initiator |
| WO2003035777A1 (en) * | 2001-10-19 | 2003-05-01 | Druckfarbenfabrik Gebr. Schmidt Gmbh | Intaglio printing process using radically curable printing inks |
| US6787583B2 (en) | 2001-05-21 | 2004-09-07 | Sicpa Holding S.A. | UV curing intaglio ink |
| US7048651B2 (en) | 1998-10-06 | 2006-05-23 | Callaway Golf Company | Golf Ball |
| US7686443B2 (en) * | 2002-07-09 | 2010-03-30 | Sericol Limited | Printing ink for ink-jet printing |
| CN104736647A (en) * | 2012-08-31 | 2015-06-24 | 惠普工业印刷有限公司 | Photocurable ink composition |
| WO2015183719A1 (en) | 2014-05-29 | 2015-12-03 | Sun Chemical Corporation | Water-based uv inkjet ink |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0077074A1 (en) * | 1981-10-13 | 1983-04-20 | DeSOTO, INC. | Ultraviolet curable basecoats for vacuum metallization |
| EP0155704A2 (en) * | 1984-03-23 | 1985-09-25 | Union Carbide Corporation | Blends of cyclic vinyl ether containing compounds and urethane acrylates |
-
1991
- 1991-06-07 GB GB9112334A patent/GB2256874B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0077074A1 (en) * | 1981-10-13 | 1983-04-20 | DeSOTO, INC. | Ultraviolet curable basecoats for vacuum metallization |
| EP0155704A2 (en) * | 1984-03-23 | 1985-09-25 | Union Carbide Corporation | Blends of cyclic vinyl ether containing compounds and urethane acrylates |
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|---|---|---|---|---|
| EP0756609A4 (en) * | 1994-04-19 | 1998-12-02 | Univ Lehigh | PRINTING INK COMPOSITIONS, METHODS OF MAKING AND USES THEREOF |
| GB2305183B (en) * | 1995-09-18 | 1999-10-06 | Lisco Inc | Game ball with UV curable ink indicia on its surface |
| GB2305183A (en) * | 1995-09-18 | 1997-04-02 | Lisco Inc | UV curable ink for game ball and method of printing |
| US6179730B1 (en) | 1995-09-18 | 2001-01-30 | Spalding Sports Worldwide Inc. | Game ball with logo formed from UV ink |
| US6149983A (en) * | 1995-09-18 | 2000-11-21 | Spalding Sports Worldwide, Inc. | UV curable ink containing aluminum trihydroxide |
| US5854300A (en) * | 1996-04-02 | 1998-12-29 | Sericol Limited | Printing ink |
| GB2311787B (en) * | 1996-04-02 | 2000-04-05 | Sericol Ltd | A printing ink |
| GB2311787A (en) * | 1996-04-02 | 1997-10-08 | Sericol Ltd | Printing Ink |
| GB2314851A (en) * | 1996-07-02 | 1998-01-14 | Sericol Ltd | A jet ink |
| GB2314851B (en) * | 1996-07-02 | 2000-03-15 | Sericol Ltd | An ink jet ink |
| EP0849728A3 (en) * | 1996-12-20 | 1999-01-07 | Mitsui Chemicals, Inc. | Optical recording medium |
| WO1998032780A1 (en) * | 1997-01-23 | 1998-07-30 | Dsm N.V. | Liquid curable resin composition |
| US6099415A (en) * | 1997-02-27 | 2000-08-08 | Acushnet Company | Ultraviolet radiation curable inks for game balls, golf balls and the like |
| US6013330A (en) * | 1997-02-27 | 2000-01-11 | Acushnet Company | Process of forming a print |
| US6248804B1 (en) | 1997-02-27 | 2001-06-19 | Acushnet Company | Ultraviolet and or/ visible light curable inks with photoinitiators for game balls, golf balls and the like |
| WO1999007796A1 (en) * | 1997-08-05 | 1999-02-18 | Sericol Limited | An ink jet ink |
| US6627677B2 (en) | 1997-08-05 | 2003-09-30 | Sericol Limited | Ink jet inks and methods |
| US6326419B1 (en) | 1997-08-05 | 2001-12-04 | Sericol Limited | Ink jet ink |
| US6428862B1 (en) | 1998-04-28 | 2002-08-06 | Canon Kabushiki Kaisha | Ink, ink-jet recording method using the same, and photopolymerization initiator |
| EP0953613A3 (en) * | 1998-04-28 | 2003-09-24 | Canon Kabushiki Kaisha | Ink, ink-jet recording method using the same, and photopolymerization initiator |
| US6500875B2 (en) | 1998-04-28 | 2002-12-31 | Canon Kabushiki Kaisha | Ink, ink-jet recording method using the same, and photopolymerization initiator |
| US7048651B2 (en) | 1998-10-06 | 2006-05-23 | Callaway Golf Company | Golf Ball |
| EP1561792A1 (en) * | 1998-10-29 | 2005-08-10 | Agfa-Gevaert | New ink compositions for ink jet printing |
| US6310115B1 (en) | 1998-10-29 | 2001-10-30 | Agfa-Gevaert | Ink compositions for ink jet printing |
| USRE40847E1 (en) | 1998-10-29 | 2009-07-14 | Agfa-Gevaert | Ink compositions for ink jet printing |
| EP0997508A1 (en) * | 1998-10-29 | 2000-05-03 | Agfa-Gevaert naamloze vennootschap | New ink compositions for ink jet printing |
| EP1561791A1 (en) * | 1998-10-29 | 2005-08-10 | Agfa-Gevaert | New ink compositions for ink jet printing |
| GB2357514A (en) * | 1999-12-23 | 2001-06-27 | Sericol Ltd | An ink for decoration of paper substrates for poster displays |
| WO2001048102A1 (en) * | 1999-12-23 | 2001-07-05 | Sericol Limited | An ink for decoration of paper substrates for poster displays |
| EP1164149A1 (en) * | 2000-06-15 | 2001-12-19 | Tarkett Sommer S.A. | Compositions based on emulgated UV-crosslinkable resins and their application as varnish layer for floor and wall coatings |
| RU2235108C1 (en) * | 2000-06-15 | 2004-08-27 | Таркетт Соммер С.А. | Compositions based on emulsified ultraviolet-cured resins and employment thereof as varnish layer for floor and wall finishing |
| CZ304819B6 (en) * | 2000-06-15 | 2014-11-19 | Tarkett Sas | Composition based on emulsified UV-curable resins |
| WO2001096431A1 (en) | 2000-06-15 | 2001-12-20 | Tarkett Sommer S.A. | Compositions based on emulsified uv-curable resins and use thereof as varnish coating for flooring and wall finish |
| US7368485B2 (en) | 2001-01-29 | 2008-05-06 | Sericol Limited | Printing ink |
| GB2371551A (en) * | 2001-01-29 | 2002-07-31 | Sericol Ltd | A Printing Ink |
| EP1358283B2 (en) † | 2001-01-29 | 2007-01-24 | Sericol Limited | A printing ink |
| GB2371551B (en) * | 2001-01-29 | 2003-07-30 | Sericol Ltd | A printing ink |
| US7572487B2 (en) * | 2001-01-29 | 2009-08-11 | Sericol Limited | Printing ink |
| US6787583B2 (en) | 2001-05-21 | 2004-09-07 | Sicpa Holding S.A. | UV curing intaglio ink |
| WO2003035777A1 (en) * | 2001-10-19 | 2003-05-01 | Druckfarbenfabrik Gebr. Schmidt Gmbh | Intaglio printing process using radically curable printing inks |
| US7686443B2 (en) * | 2002-07-09 | 2010-03-30 | Sericol Limited | Printing ink for ink-jet printing |
| CN104736647A (en) * | 2012-08-31 | 2015-06-24 | 惠普工业印刷有限公司 | Photocurable ink composition |
| US9441125B2 (en) | 2012-08-31 | 2016-09-13 | Hewlett-Packard Industrial Printing Ltd. | Photo-curable ink composition |
| WO2015183719A1 (en) | 2014-05-29 | 2015-12-03 | Sun Chemical Corporation | Water-based uv inkjet ink |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2256874B (en) | 1994-12-14 |
| GB9112334D0 (en) | 1991-07-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19960607 |