CA1050692A - Photopolymerizable compounds stabilized against premature gelation with copper compounds and thiocarbamates - Google Patents

Photopolymerizable compounds stabilized against premature gelation with copper compounds and thiocarbamates

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Publication number
CA1050692A
CA1050692A CA221,041A CA221041A CA1050692A CA 1050692 A CA1050692 A CA 1050692A CA 221041 A CA221041 A CA 221041A CA 1050692 A CA1050692 A CA 1050692A
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CA
Canada
Prior art keywords
composition
copper
compound
thiocarbamate
photopolymerizable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
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CA221,041A
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French (fr)
Inventor
Thor P. Jondahl
George Pasternack
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Continental Can Co Inc
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Continental Can Co Inc
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Filing date
Publication date
Priority claimed from US05/539,199 external-priority patent/US3956235A/en
Application filed by Continental Can Co Inc filed Critical Continental Can Co Inc
Application granted granted Critical
Publication of CA1050692A publication Critical patent/CA1050692A/en
Expired legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • 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
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Polymerisation Methods In General (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE

Photopolymerizable ethylenically unsaturated ester compositions useful as coating and printing ink vehicles, and especially pigmented coatings and inks, are stabilized to pre-mature gelation by incorporating therein a small but effective amount of a stabilizing combination of a copper containing com-pound and a thiocarbamate compound.

Description

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~ liS invention relates to photopolymerizable composi-tions which are useful as coating and printing ink vehicles and more particularly to pigrnented photopo:Lymerizable coatings and inks which are stable to premature gelation.
Printing inks and coatings prepared using photopolymeriz-able vehicles are known to the art which can be polymerized and dried by exposure to ultraviolet radiation as example, U.S.
2,453,769, 2,453,770, 3,013,895, 3,051,591, 3,326,710, 3,511,710, ;
3,772,062 and 3,804,735.
These photopolymerizable inks and coatings are generally pigmented ethylenically unsaturated polyester compositions. When photoinitiators are incorporated in the composition, thin liquid ~ ;
films of the photopolymerizable composition can be cured to a hard film within 1 second or less using medium pressure mercury lamps.
The use of photopolymerizable inks and coatings eliminates the use of volatile organic solvents and the high cost and time of oven-baking which has heretofore been the conventional prac-tice for drying and hardening inks and coatings.
In formulating inks ùsing photopolymerizable unsaturated ~ , polyester vehicles, it was found that for some unexplainable reason, when the ester vehicles, which are normally stable to gelation at room temperature were pigmented with colorants, the ester vehicle self-polymerized within a short time to form undesirable gels. The formation of gels in the ink or coating formulation substantially destroys the commercial utility of the formulation. Preventing the gelation of the pigmented formulation or at least extending the time in which a pigmented composition will gel is important in commercial .

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practice as several weeks storage is often required between formulation of the ink or pigmented coating and actual use of the formulation in printing and coating applicakions.
In accordance with the present invention there is provided photopolymerizable compositions which exhibit impro~ed stability to gel formation and which may be rapidly polymerized and hardened by exposure to a source of ultraviolet radiation, the compositions being comprised of an ethylenically unsaturated ester and a small but effective amount of a stabilizing combination of a copper con-taining compound and a thiocarbamate compound having the formula:

M ~ S - C - N f~CH2)Xl 1 ~, . S n wherein M is x~CH2) `2~N-, x(CH2 R ,N-C-S-, ~NH4 ) or a metal cation having a valence of l to 3 and each of R, Rl, R2, and R3 (same or different) are hydrogen, aryl, saturated and unsaturated 2~ alkyl groups having 1 to 20 carbon atoms, aralkyl or alkaryl groups having 7 to 15 carbon atoms and amino, sulfo-and oxy-substituted alkyl and aryl groups, n is an integer of 1 to 3 and x is an integer from 0 to 1. Thus, the alkyl groups represented by R, Rl, R2 and R3 may be straight chain aliphatic groups, branched chained aliphatic groups and cyclic aliphatic groups or form heterocyclic ring structures with the nitrogen atom present in the thiocarbamate compound.
When the combination of a copper containing compound and a thiocarbamate compound of the type disclosed is incorporated in ethylenically unsaturated esters and especially pigmented esters, . . . . .
, . , . , . ~., , . - : .

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in accordance with the practice of the present invention, the period of time during which the photopolymerizable ester will withstand gel ~ormation is extended to commercially acceptable levels. As will hereina-fter be illustrated, when either member of the stabilizing com~ination is omitted from the photopolymer-able composition, no appreciable diminution in gel time is obtained.
The term "ethylenically unsaturated ester compound" as used herein means, monohydric alcohol esters of ~ ethylenically unsaturated acids, polyesters obtained by the reaction of an ~ , ~ -ethylenically unsaturated mono- or dibasic acid with a polyhydric alcohol having 2 to 6 hydroxyl groups or a polyepoxide containing at least 2 reactive epoxy groups in the polyepoxide molecule and mixtures thereof.
Included within the meaning of ~ ethylenically unsaturated acid are unsaturated monocarboxylic acids-having from ,.
3 to 6 carbon atoms, e.g. acrylic acid, methacrylic acid, crotonic acid and sorbic acid and unsaturated dicarboxylic acids having 4 to 10 carbon atoms, e.g. maleic acid, tetrahydrophthalic acid, fumaric acid, glutaconic acid, itaconic acid and the like.
Illustrative of photopolymerizable ethylenically un-saturated polyesters useful in the practice of the present invention are acrylic acid and methacrylic acid esters of aliphatic polyhydric alcohols such as, for example, the di- and polyacrylates and the di-and polymethacrylates of ethylene glycol, polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, tetramethylene glycol, the correspondlng ether glycols, triethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and polypentaerythritols.
Typical unsaturated polyesters include, but are not limited to, trimethylolpropane triacrylate, trimethylolethane triacrylate, triethylolpropane trimethacrylate, trimethylolethane trimetha-., .

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acrylate, tetramethylene glycol dimethacrylate, ethylene ylycol dimethacryLate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, pentaery-thritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, and dipentaery-thritol dimethacrylate.
A preferred class of ethylenically unsaturated polyester compounds useful in the practice of the present invention are the reaction products of a polyepoxide having at least two reactive groups in the polyepoxide molecule and an ethylenically un- ~
saturated acid such as the ~ ethylenically unsaturated mono- ~;
; carboxylic acids having 3 to 6 carbon atoms and ~, ~-ethylenic~
ally unsaturated dibasic acids having 4 to 10 carbon atoms previously discussed. These polyepoxide derived polyesters are well known to the art, e.g. U.S. 3,637,618, U.S. 3,408,422, U.S. 3,373,075, and Br. 1,241,851.
Typical examples of polyepoxide compounds useful in the preparation of ethylenically unsaturated polyesters preferred in ` the practice of the present invention include epoxidized poly-butadiene (Oxiron 2001*), epoxidized linseed oil (Epoxol 9-5*), 1,4-butylene diglycydyl ether (RD-2), vinylcyclohexene diepoxide (Epoxide 206), resorcinol diglycidyl ether (Kopoxite 159*), . .
Bisphenol A diglycidyl ether (DER-332), s-tetraphenylethane tetra-glycidyl ~ther (Epon 1031*), novalac resin polyglycidyl ether (DEN 438), dicyclopentadiene diepoxide (Epoxide 207) and dipentene dioxide.
Polyesters especially preferred in the practice of the present invention are polyesters prepared by reacting Bisphenol A diglycidyl ether, i.e. the diglycidyl ether of 2,2-bis trademark 4 :

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(4-hydroxyphenyl propane) with an ethylenically unsaturated mono-carboxylic acid such as acrylic or methacrylic acid at a molar ratio of about 1:2 to prepare the diacrylate reaction product or with an ethylenically unsaturated dicarboxylic acid such as itaconic acid at equal molar ratios.
The Bisphenol A diglycidyl ether diacrylate may be blended with the ~isphenol A diglycidyl ether itaconate as well as other ethylenically unsaturated compounds and especially acrylate ester compounds to prepare photopolymerizable mixtures ha~ing the physical properties suitable for printing inks and coatings.
Examples of thiocarbamate compounds useful i~ the practice of the present invention include, tetramethylthiuram disul~ide, - tetraethylthiuram disulfide, tetrapropylthiuram disulfide, tetrabutylthiuram disulfide, tetradecylthiruam disul-~ide, tetrahexadecylthiuram disulfide, tetracicosylthiuram disulfide, l-methyl-l-propyl-6-butyl~6- methyl thiuram disulfide, l-propyl-l-butyl-6-methyl-6-t-butyl thiuram disul~ide, dihexamethylene thiuram disulfide, dipentamethylene thiuram disul~ide, piperdinium pentamethylene dithiocarbamate, piperdinium dibutyl dithiocarbamate, piperdinium dicyclohexyl dithiocarbamate, piperdinium di(3-: oxycyclohexyl~ dithiocarbamate, metal thiocarbamates as for example, nickel dipropyldithiocarbamate, nickel dibutyldithio-carbamate, nickel didecyldithiocarbamate, zinc dimethyldithio-carbamate, zinc dibutyldithiocarbamate 9 zinc dihexyldithiocarbamate, - sodium dibutyl dithiocarbama*e, copper dimethyl dithiocarbamate, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, copper diamyldithiocarbamate, copper dioctadecyldithiocarbamate, copper diphenyldithiocarbamate, copper dibenzyldithiocarbamate, copper di(orthotolylaminoethyl) dithiocarbamate, copper dicyclohexyldithiocar~amate, ammonium dipropyldithiocarbamate, potassium dihexyldithiocarbamate, calcium dihexyldithiocarbamate, zirconium diethyldithiocarbamate, cobalt dibutyldithiocarbamate, .

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~ ~5~ 2 antimony dibutyldithiocarbamate, bismuth dimethyldithiocarbamate, lead dimethyldithiocarbamate, tin dibutyldithiocarbamate, copper dicyclopentyldithiocarbamate, copper l-butyl-l-cyclohexyl-7-butyl-7-cyclohexyl ditlliocarbamate, copper di(3-oxacyclohexyl) dithio-carbamate, copp~r di~4-oxacyclohex~l) dithiocarbamate, copper di(3-thiocyclohexyl) dithiocarbamai:e, copper di(4-azacyclohexyl) dithiocarbamate, copper l-butyl-l- (3-oxacyclohexyl)-7-butyl-i-(3-oxacyclohexyl) dithiocarbamate, copper di(4-pyridyl) dithio-carbamate, copper di (4-n,n-dimethyl anilino) dithiocarbamate, copper di(4-anisyl) dithiocarbamate, copper di(4-thioanisyl) dithiocarbamate, and copper di~3-furanyl) dithiocarbamate.
The thiocarbamate compounds may be incorporated in the photopolymerizable ester compositions at concentrations ranging from 0.10 to about 1.0% by weight. Higher concentrations may be used if necessary, but concentrations substantially in excess of 1.0% by weight have been found to have a significant retarding effect on the speed at which the photopolymerizable composition will be cured by ultraviolet radiation.
- Copper containing compounds useful in the practice of the present invention include any copper containing compound which - is compatible with the photopolymerizable ester composition.
Illustrative examples of copper containing compounds useful in the practice of the present invention include the inorganic acid cupric salts such as cupric chloride, cupric nitrate, cupric phosphate, cupric sulfate, cupric chromate, organic acid cupric salts as for example cupric napthenate, salts having the formula Cu (OOCR)2 wherein R is a saturated or unsaturated straight or branched chain aliphatic substituent having about 2 to 20 carbon atoms such as cupric acetate, cupric ~i 30 propionate, cupric butyrate, cupric hexoate, cupric octoate, cupric laurate, cupric palmitate, cupric stearate, and cupric oleate.
Cuprouc compounds such as inorganic acid cuprous salts and .:.. . :, ,. :.

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organic aci~ c-lprous salts such as cuprous chloride, cuprous acetate and the like are also inclllded within the meaning of copper containing compounds and are useful in the practice of the present invention.
In ~he event that photopolymerizable compositions are pigmented with copper containing pigments such as copper phthalocyanine, the separate inclusion of a copper compound in the photopolymerizable composition is not generally required. As will hereînafter be illustrated, photopolymerizable compositions pigmented with copper containing pigments are stabilized to gel formation merely by the addition thereto of a non-copper containing thiocarbamate compound. However, if these same non-copper thio-carbamate compounds are incorporated in a photopolymerizable composition in which copper ion is absent, effective gel stabiliz-ation generally does not occur. When the photopolymerizable composi-tion is pigmented with a colorant that does not contain copper cation, the stabilizing combination is most conveniently incorporated in the photopolymerizable composition by the singular addition of a copper ; salt of a thiocarbamate compound as for example copper di-butyldithiocarbamate.
The copper cation is desirably present in the photo-polymerizable composition in an amount about stoichiometrically equal to the amount of thiocarbamate compound incorporated in the photopolymerizable composition. For example, when cupric compounds are incorporated :in the photopolymerizable composition, the molar ratio of Cu~+ ion to thiocarbamate radical is generally about 1:2.
When cuprous compounds are incorporated in the photopolymerizable ; composition the molar ratio of Cu+ ion to thiocarbamate radical is generally about 1:1. It has been determined that the molar ratio of Cu++ ion to thiocarbamate radical may vary -from 1:2, if the ratio is appreciably greater than 1:2, as for example, 1:1? an appreciable diminution in stabilizing effectiveness is encountered.

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Generally a molar ratio of Cu~ ion to thiocarbamate radical of about 0.8:2 to 1.5:2 will give bene~icia:L results, and a molar ratio ~f about 1:2 to 1.2:2 is preferred. The molar ratio o~ Cu~ ion to thiocarbamate radical may vary from about 0.8:1 to 1.2:1.
When copper containing pigments are used as Q source of the copper cation for the stabilizing c:ombination, the pigments although they may be incorporated in photopolymerizable ester ; compositions at relatively high concentrations, e.g. 5 to 25% by weight of the ester composition, are substantially insolwble in the ester composition and do not furnish an excessive amount o~ copper ion to the ester composition. It has been found in practice that by dispersing copper containing pigments in ethylenically un-saturated photopolymerizable ester compositions 9 a sufficient amount of copper ion is made available to the composition by the pigment to form an effective stabilizer combination when used cojointly with 0.1 to 1.0% by weight of a non-copper containing thiocarbamate compound.
Illustrative examples of materials useful as pigments for photopolymerizable ester based printing inks include copper phthalocyanine blue (Pigment Blue 15), copper polychlorophthalo-cyanine green, copper bromochlorophthalocyanine, carbon black, Chrome Yellow #40-4500 (American Cyanamid), Naphthanil Red Dark #RT-539-D (Du Pont) 9 Valencia Moly Orange #YE-421-D (Du Pont), Watchung Rubine #RT-709-D (Du Pont), Sahara Yellow #X-2864 (Hercules), Bon Maroon Light #RT-533-D (Du Pont), Phthalocyanine Blue #55-3295 ~American Cyanamid), Duplex Barium ~ithol #20-4480 (American Cyanamide), Paliofast Blue (non-metallic) #7560 (BASF), Rhodamine B #20-7470 (American Cyanamid), Monastral Red B #RT-790-D
(Du Pont) and Supercarbovar #SRS-652 (Cabot).
Photoinitiators may be incorporated in the ester compositions ` used as vehicles for photopoIymerizable printing inks and coatings to accelerate the speed at ~hich the inks and coatings harden on ., .

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exposure to ultraviolet light. Illustrative examples of suitable photoinitiators include benzophenone, Michler's ketone (4,4'-bis dimethylamino benzophenone) and mixtures thereof. The photo-initiators are incorporated in the photopolymerizable compositions at a concentration of 0.1 to 5$ by weight.
In general, printing inks prepared using the pigmented photopolymerizable compositions of the present invention are prepared in the same manner as conventional printing inks.
Generally, the printing inks contain about 30 to about 95 percent by weight of the photopolymeri7able composition and about 5 to about 70 percent by weight of the pigment.
- In printing metal surfaces with ultraviolet curable printing inks, the ink is applied using a printing press conventionally used ~or printing on metal substrates. Once the metal substrate, generally in the form of a sheet is printed, the substrate is positioned to pass under a source of ultraviolet light to dry and harden the ink. In most instances, the ultra-violet light source is maintained at about 0.5 to about 5 inches from the printed substrate undergoing irradiation.
; 20 Rapid drying of the inks using the stabilized photoinitiatedcompositions of the present invention is effected within a second of exposure to ultraviolet light emitted from an artificial source havlng a wave length in the range between 4000A and 1800A.
In the printing of metal coil stock for beverage container manufacture where extremely high speed drying o-f the ink ~i.e.
within one second) is required, mercury vapor discharge lamps, ` especially of the medium pressure type are used as a source o ultraviolet radiation. The output of commercially available medium pressure mercury vapor lamps varies between 100 to 200 watts per linear inch of lamp surface.
The present invention is illustrated by the Examples which follow:
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For purposes of comparison, in a separate series of tests run in accordance with the procedure of Exanlple 11 a number of known stabilizer compounds as well as compounds closely related to the compounds used in the present invention, but outside the scope of the invention, were incorporated in the pigmented ink vehicle and these comparison ink compositions were also tested for gel stability. The results of these comparative tests, designated by the symbol "C", are aIso summarized in Tables I and II. Also tests in which no stabilizer compounds were incorporated in the pigmented ink vehicle were also run and are also designated by the symbol "C"
in the Tables.

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T~sLE I
Concen- Gellakion Time Test tration ~Minutes) No. Stabilizer Wt. % 40 80100 120 160 ... . . . ... . _ . _ _ . . _ 1 Zinc dibutyldithiocarbamate 0.25 Gel 2 Zinc dibutyldithiocarbamate 1.0 Gel 3 Nickel dibutyldithiocarbamate 0.5 Gel
4 Nickel dibutyldithiocarbamate 1.0 Gel
5 Tetraethylthiuram disulfide 0.2S Gel
6 Tetraethylthiuram disulfide 1.0 Gel
7 Sodium N,N-diethyldithiocarbamate 1.0 Gel
8 Piperidinium pentamethylene 1.0 Gel dithiocarbamate
9 l-Pyrrolidenecarbodithioc acid 0.25 Gel ammonium salt
10 l-Pyrrolidenecarbodithioc acid 1.0 Gel -~ ammonium salt :
- Cl ~one 0 Gel C2 p-Methoxyphenol 1.0 Gel C3 p-Methoxyphenol 2.0 Gel C4 2,6-di-tert,-butyl-4-methylphenol 1.0 Gel ~ -C5 2,6-di-tert,-butyl-4-methylphenol 2.0 Gel C6 1,1,3,3-tetraethyl-2-thiourea 1.0 Gel ~: C7 N,N-Dimethylthioformamide 1.0 Gel C8 Zinc isopropyl xanthate 1.0 Gel ~ :~

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TABL~ II
-Concen-Gellation Time Test tratlon (Minutes) No. Stabilizer Wt. % Pigment 20 ~0 60
11 Zinc dibutyl dithiocarbamate1.0 CPG Gel Cg 2,6-di-t-butyl-4-methylphenol 1.0 CPG Gel C10 2,6-di-t-butyl-4-methylphenol 2.0 CPG Gel Cll None 0 CPG Gel C12 Zinc dibutyldithiocarbamate0.25 NPB Gel C13 ~ickel dibutyldithiocarbamate 0.25 NPB Gel 14 0 NPB Gel ... ..
The data in Tables I and II indicate that copper phthalocyanine pigmented photopolymeriza~le compositions stabilized with a thiocarbamate compound in accordance with the practice of the present invention exhibit superior storage stability when compared to copper phthalocyanine pigmented photopolymerizable compositions stabilizéd with compounds outside the scope of the invention as well as photopolymerizable compositions pigmented ~ith non-copper con-taining pigments and thiocarbamate compounds.
EXAMPLE II
~ .
A zinc dibutyldithiocarbamate stabilized, copper phthalocyanine blue pigmented photopolymerizable ~omposition composed of the composition used in Test number 1 of Table 1 was applied to steel plate of the type used in the manufacture of steel beverage containers using a number 10 draw bar which evenly dis-tributed the composition as a thin film on the plate.
After application o~ the stabilized pigmented photo-polymerizable composition, the coated plate was placed under a medium pressure mercury lamp at a distance of about 1.0 inch from the lamp sur~ace.

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The radiation emitted by the lamp was approximately 200 watts/in. of lamp surface. The coated plate when exposed to the ultraviolet radiation dried in 0.6 seconds.
EXAMPLE III ?
A series of accelerated ink vehicle storags stability tests were conducted following the procedure of Example I with the exception that 17.565 grams of ink vehicle were used, having incorporated therein 12 percent by weight, based in the weight o~
the vehicle, of a variety of different pigments which did not con-10 tain copper ion and 0.20 and 0.50 percent by weight of copper dibutyldithiocarbamate ~CDBDTC). Ihe results of these accelerated storage stability tests are recorded in Table III below.
For purposes of comparison, in a separate series of ~- accelerated storage stability test, 0.25~ zinc dibutyldithiocarbamate ~ZDBDTC) and 0.50% by weight copper napthenate (CNAP) were separately incorporated in the differently pigmented vehicles.
The results of these comparative accelerated storage stability tests are also recorded in Table III below.

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;C~2 TABLE III_ G.LLLATION TIME (minutes) Pigmented Pigmented Pigmented Pigmented Vehicle Vehicle Vehicle Vehicle Pigment Incorporated + ~ ~
In CDBDTC ZDBDTC CNAP No Stabilizer Vehicle 0.2% 0.5~0~2'i% 0.50% Added _.
None 150* 220 60 20 80 Duplex Barium Lithol 120 370 40 30 40 Rhodamine B 180 270 20 20 40 Naphthanil Red Dark 160 310 40 20 40 Watchung Red 160 410 40 10 40 Bon Maroon Light 120 270 80 20 40 Sahara Yellow 210 390 60 10 60 .
Paliofast Blue 120 290 60 20 80 ; Monastral Red B 180 430 60 20 60 : Chrome Yellow 120 200 20 10 20 Moly Orange 210 430 20 10 40 Moly Orange - - 20~*
:
. Moly Orange - - 20***
.- ' ~.
* 0.05% by weight CDBDTC used.
** 1% by weight ferric dibutyldithiocarbamate substituted for 0.25% by weight ZDBDTC.
*** 1% by weight silver dibutyldithiocarbamate substituted for 0.25~ by weight ZDBDTC.

The data in Table III lndicates that photopolymerizable compositions pigmented with pigments which do not contain copper ``
must have a combination of a copper containlng compound and a thiocarbamate compound incorporated therein to stabilize the pigmented composition to gel formation.

~ ~ S0 ~3 EXAMPLE IV
A series of accelerated ink vehicle storage stability tests l~ere conducted following ~he procedure of Example III using un-pigmented vehicle and moly orange pigmented vehicle. Zinc di-butylditlliocarbamate at a concentration of 0.25% by weight ~equal to 3.16 x 10-4 moles dibutyldithiocarbamate) and varying amounts of C~C12 were incorporated in the vehicles. The results of these accelerated storage stability tests are recorded in Table IV below.
TABLE IV
GELLATION TIME (minutes) Concentration Moles Test CuC12 Cu'~ Unpigmented Pigmented No. (Wt.~) x10-4 Vehicle Vehicle 2 0.05 0.88 160 160 `
` 3 0.10 1075 180 160 4 0.20 3.52 60 40 0.30 5.28 20 40 6 0.40 7.04 20 40 ` ~ -7 0.50 8.80 20 40 ' The results of the accelerated ink vehicle storage stability tests recorded in Table IV indicate that combinations of dibutyldi-thiocarbamate compounds and copper containing compounds are ; effective stabilizer combinations for ethylenically unsaturated photopolymerizable compositions (Tests nos. 2-3). However when the molar amounts of Cu+~ and dibutyldithiocarbamate radical are substantially greater than 1:2, e.g. 1:1 or greater as in Tests numbers 4-7, the stabilizing effect of the combination is sub-stantially reduced to an ineffective state.

. .
', .~ .
.

:: ~ . ..
. . . - .
:., . : .
~ , .. ~ . . . . ' E_~MPLE V 1 05~D~92 In a series of accelerated lnk vehicle storage stability tests the procedure o-f Example III was repeated with the exception that a variety o-f different pigments were incorporated in the vehicle along with a stabilizing combination of 0.25% by weight zinc dibutyldithiocarbamate (ZDBDTC) and 0.5% by weight copper napthenate (CNAP). The results of these accelerated gel stability tests are recorded in Table V below.
For purposes of comparison, in a separate series of accelerated storage stability tests 0.25% by weight ZDBD~C and 0.50% by weight CNAP were separately incorporated in the different pigmented vehicles. The results of these comparative accelerated gel stability tests are also recorded in Table V below.
TABLE V
TIME FOR GELLATION ~Minutes) Vehicle ZDBDTC Vehicle Vehicle + + ~ .
20 Pigment CNAP ZDBDTC CNAP Vehicle ;~ ~
___ _ :
None 220 60 20 80 DuPlex Barium 140 40 20 43 Lithol Rhodamine B 160 20 20 40 Naphanil Red 240 40 40 40 Dark Watching Rubine 240 40 20 40 Bon Maroon Light 140 80 40 40 Monastral Red B 240 60 20 60 Chrome Yellow 80 20 20 40 Moly Orange 80 20 20 40 Sahara Yellow 240 60 20 60 Cyano Blue 120 120 20 20 (contains Cu) Cyano Blue 220 60 20 80 : . ~

~5~V~9z EXAMPLE VI
.
In a series of acceleratecl ink vehicle storage stability tests the procedure of Example III was repeated using unpigmented vehicle and moly orange pigmented vehicle. A stabilizing combination of 0.25% by weight zinc dibutyldithiocarbamate (ZDBDTC) and 0.05% by weight CuCl was separately incorporated in the vehicles. The results of these accelerated gel stability tests are recorded in Table VI below.
F'or purposes of comparison, in a separate series of - l0 accelerated storage stability tests, 0.05% by weight CuCl has separately incorporated in the vehicles. The results of these - comparati~e accelerated gel stability tests are also recorded in Table VI below. `!
TABLE VI ~ -TIME FOR GELLATION (Minutes) Vehicle +
ZDBDTC Vehicle ,,, +
20 Pigment CuCl CuCl Vehicle ,: - - - ~ .
None 200 6Q 60 Mo1y Orange 140 20 -'''- ,': ,' ,- ' ' . .

' : ':: . ' `: `

Claims (27)

C L A I M S

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A photopolymerizable composition stabilized to gel formation comprised of an ethylenically unsaturated ester and a stabilizing amount of copper containing compound and a thio-carbamate compound having the formula wherein M is selected from the group consisting of , (NH4+) and a metal cation having a valence of 1 to 3 and each of R, R1, R2 and R3 are selected from the group consisting of hydrogen, aryl, alkyl groups having 1 to 20 carbon atoms, aralkyl and alkaryl groups having 7 to 15 carbon atoms and amino-,sulfo-and oxy-substituted alkyl and aryl groups, n is an integer of 1 to 3 and x is an integer of 0 to 1.
2. The composition of claim 1 wherein the photopolymer-izable composition contains a pigment.
3. The composition of claim 1 wherein the copper containing compound is a pigment containing copper.
4. The composition of claim 1 wherein the copper containing compound is the copper salt of an organic or inorganic acid.
5. The composition of claim 4 wherein the copper salt is CuC1.
6. The composition of claim 4 wherein the copper salt is CuC1.
7. The composition of claim 4 wherein the copper salt is copper napthenate.
8. The composition of claim 2 wherein the photopolymerizable composition contains about 5 to 70 percent by weight of the pigment.
9. The composition of claim 1 wherein the copper containing compound incorporated in the photopolymerizable composition contains copper cation in an amount about stoichiometrically equal to the thiocarbamate compound incorporated in the photopolymerizable composition.
10. The composition of claim 1 wherein the molar ratio of cupric ion to thiocarbamate compound present in the photopolymerizable composition varies from about 0.8:2 to 1.5:2.
11. The composition of claim 1 wherein the thiocarbamate compound is incorporated in the photopolymerizable composition at a concentration at about 0.10 to about 1.0 percent by weight.
12. The composition of claim 1 wherein the thiocarbamate compound is a metal dialkyldithiocarbamate.
13. The composition of claim 12 wherein the metal dialkyldi-thiocarbamate compound is zinc dibutyldithiocarbamate.
14. The composition of claim 12 wherein the metal dialkyldi-thiocarbamate compound is nickel dibutyldithiocarbamate.
15. The composition of claim 12 wherein the metal dialkyldi-thiocarbamate compound is sodium N,N-diethyldithiocarbamate.
16. The composition of claim 1 wherein the thiocarbamate compound is piperidinium pentamethylene dithiocarbamate.
17. The composition of claim 1 wherein the thiocarbamate is l-pyrrolidenecarbodithioc acid ammonium salt.
18. The composition of claim 1 wherein the thiocarbamate compound is tetraethylethiuram disulfide.
19. The composition of claim 1 wherein the copper containing compound and the thiocarbamate compound are both a copper dialkyldithiocarbamate.
20. The composition of claim 19 wherein the copper dialkyldithiocarbamate is copper dibutyldithiocarbamate.
21. The composition of claim 1 wherein the ethylenically unsaturated ester is the reaction product of a polyepoxide having at least two reactive groups in the polyepoxide molecule and an acid selected from the group consisting of 2 , .beta. -ethylenically unsaturated mono carboxylic acids having 3 to 6 carbon atoms and 2 ,.beta. -ethylenically unsaturated dibasic acids having 4 to 10 carbon atoms.
22. The composition of claim 1 wherein the unsaturated compound is the reaction product of a polyhydric alcohol having 2 to 6 carbon atoms and an acid selected from the group consisting of 2 , .alpha. -ethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and 2 , .beta. -ethylenically unsaturated dibasic acids having 4 to 10 carbon atoms.
23. The composition of claim 21 wherein the polyepoxide is the diglycidyl ether of bisphenol A.
24. The composition of claim 21 wherein the acid is acrylic acid.
25. The composition of claim 21 wherein the acid is itaconic acid.
26. The composition of claim 22 wherein the alcohol is pentaerythritol.
27. The composition of claim 22 wherein the alcohol is polyethylene glycol.
CA221,041A 1974-03-18 1975-02-28 Photopolymerizable compounds stabilized against premature gelation with copper compounds and thiocarbamates Expired CA1050692A (en)

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