WO1981000011A1 - Poly(ethylenically unsaturated alkoxy)heterocyclic compounds and crosslinked polymeric coatings - Google Patents

Poly(ethylenically unsaturated alkoxy)heterocyclic compounds and crosslinked polymeric coatings Download PDF

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Publication number
WO1981000011A1
WO1981000011A1 PCT/US1980/000612 US8000612W WO8100011A1 WO 1981000011 A1 WO1981000011 A1 WO 1981000011A1 US 8000612 W US8000612 W US 8000612W WO 8100011 A1 WO8100011 A1 WO 8100011A1
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compound
group
carbon atoms
polymeric coating
substrate
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PCT/US1980/000612
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English (en)
French (fr)
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L Wendling
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Minnesota Mining & Mfg
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Priority claimed from US06/051,877 external-priority patent/US4262072A/en
Priority claimed from US06/051,876 external-priority patent/US4249011A/en
Application filed by Minnesota Mining & Mfg filed Critical Minnesota Mining & Mfg
Priority to BR8008725A priority Critical patent/BR8008725A/pt
Priority to DE8080901348T priority patent/DE3069342D1/de
Publication of WO1981000011A1 publication Critical patent/WO1981000011A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • 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
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/14—Monomers containing only one unsaturated aliphatic radical
    • C08F16/28—Monomers containing nitrogen
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • 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
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/10—Homopolymers or copolymers of unsaturated ethers
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present invention relates to novel ethylenically unsaturated crosslinking agents and to radiation curable compositions containing these agents.
  • the invention particularly relates to ethylenically unsaturated heterocyclic crosslinking agents, to radiation curable oxygen insensitive compositions containing such agents, to alcohol or aqueous alcohol developable imaging layers containing such compositions, and to abrasion and solvent resistant layers formed from these agents.
  • crosslinking has been produced in products from ethylenically unsaturated compositions such as acrylic compositions (e.g., a methyl methacrylate composition) by incorporation of from about 1 to about 10 percent by weight of a polyacrylic substituted compound as a crosslinking agent. It is well known that such acrylic compositions generally must be polymerized in an inert atmosphere, e.g., a nitrogen atmosphere.
  • the oxygen present in air will retard or even prevent polymerization of the acrylic compos ition so that desired levels of polymerization cannot be achieved.
  • a tacky, incompletely polymerized resin or a weak, low molecular weight polyacrylate resin can be obtained.
  • compositions are useful for coatings and inks that can be cured in the presence of oxygen, these compositions are not satisfactory for coatings that are transparent and where discoloration is undesirable since the use of large amounts of photoinitiator leads to yellowing of the cured coating.
  • U.S. Patent 3,968,305 describes acrylic compositions comprising an aliphatic compound having three or more methacryloxy groups that can be polymerized to a crosslinked mar resistant coating.
  • U.S. Patent 4,014,771 teaches that by the addition of 1) 30 to 95 percent of the adduct of methacrylic acid and 2) either a polyglycidyl ether of an aromatic polyhydric compound or a polyglycidyl ester of an aromatic or aliphatic polycarboxylic acid to a polymethacryloxy compound such as that described in U.S. Patent 3,968,305, there is obtained a composition which evidently can be polymerized without the necessity of excluding air during the polymerization.
  • novel ethylenically unsaturated crosslinking agents comprising poly(ethylenically unsaturated alkoxyalkyl)heterocyclic compounds and a process for their preparation.
  • the crosslinking agents of the invention have the general formula:
  • a 1 and A 2 independently are groups having terminal ethylenic unsaturation and having the general formula:
  • R-O- is a monovalent residue (formed by removal of the active hydrogen from an -OH group) of an aliphatic terminally unsaturated primary alcohol, ROH, R having the formula:
  • E is a and c are independently an integer of 1 to 6
  • b is zero or an integer of 1 to 6
  • R 1 and R 4 are independently hydrogen or methyl
  • R 2 is preferably hydrogen but can be or wherein R 6 is preferably alkenyl but can be alkyl (each preferably having 2 to 5 carbon atoms) and can be substituted by a phenyl or carboxyl group and R 7 is an aliphatic group (of up to eight carbon atoms, e.g., alkyl) or aromatic group (preferably having up to 8 carbon atoms and more preferably a phenyl group) and R 7 is most preferably an acryloyloxyalkyl or a methacryloyloxyalkyl group, R 3 is an alkylene group having 1 to 6 carbon atoms and optionally one catenary oxygen atom; and
  • Z is a heterocyclic group of the formula:
  • X is a divalent group which is required to complete a
  • X can be or wherein R 8 , R 9 , R 10 , and R 11 are independently hydrogen or lower alkyl (of 1 to 4 carbon atoms), cycloalkyl (of 3 to 6 carbon atoms) or phenyl group
  • a 3 is an alkoxyalkyl group as defined above for A 1 and A 2 .
  • the preferred compounds of Formula I are those wherein E is m is 2 to 5, and X is These compounds are preferred because they provide not only a high crosslink density, resulting in improved solvent and abrasion resistance but also excellent adhesion and flexibility. Furthermore, these compounds are water/alcohol soluble and are photocurable to tack free surfaces in the presence of atmosphere oxygen.
  • This invention further includes energy crosslinkable compositions particularly to photocurable compositions comprising the poly(ethylenically unsaturated alkoxyalkyl) heterocyclic compounds of the present invention and a polymerization catalyst which liberates free radicals on application of energy.
  • the compounds of the invention can be prepared by the Lewis acid catalyzed addition of n moles of an ethylenically unsaturated primary alcohol to an epoxysubstituted heterocycle in accordance with the equation:
  • R, R 1 , R 3 , and Z are as defined for the compounds of Formula I, and n is 2 or 3.
  • the (polyacrylyloxy)alkoxypropylheterocyclic compounds of the invention are 5- or 6-membered ring heterocyclic compounds having preferably two (but may have three) nitrogen and preferably two (but may have three) carbonyl groups, viz. in the ring. At least one but preferably all of the ring nitrogens are substituted by a (polyacryloyloxy)alkoxypropyl group (e.g., Formula II). The substituted heterocyclic.
  • a heterocyclic compound as defined, that has one, two or three (where present) of its ring nitrogens substituted by a glycidyl group (e.g., a 2,3-epoxypropyl group), of one, two or three equivalents of a hydroxy compound that is the product of esterification of m hydroxyl groups of a polyol having (m + 1) hydroxyl groups with acrylic or methacrylic acid in accordance with the equation:
  • R 1 , R 2 , m, R 3 and X are defined above.
  • the above equation illustrates the preparation where only one of the ring nitrogens has been substituted by the glycidyl group.
  • two or three of the ring nitrogens have been substituted by glycidyl (as is most preferable)
  • two or three equivalents of hydroxy compound can be added.
  • the addition of the hydroxy compound to the glycidyl groups of the heterocyclic compound can be done in one step or in a sequence of steps in which first one and then a second and then a third glycidyl group is reacted. It is not necessary that the same hydroxyl compound be used in each of the steps.
  • the polymerizable coating composition is a heterocyclic compound having at least two glycidyl groups reacted with hydroxy compounds in which m in Formula I is at least three; that is, the hydroxy compound to be reacted with the glycidyl group of the heterocyclic compound is preferably a tri- or higher acryloyloxy or methacryloyloxy-hydroxy compound.
  • polyglycidyl heterocyclic intermediates useful in the preparation of any and all of the compounds of the present invention are disclosed in U.S. Patents Nos. 3,808,226 and 4,071,477.
  • the reaction is performed in solution.
  • it also can be performed in the absence of solvent.
  • a solution of an epoxy-substituted heterocycle can be added incrementally (over a period of time ranging from a few minutes to several hours) to a mixture of 1) an ethylenically unsaturated primary alcohol (or mixtures of ethylenically unsaturated primary alcohols), 2) an inhibitor for thermal polymerization, and 3) a Lewis acid while maintaining the temperature of the mixture at 50 to 120°C, preferably about 80 to 100°C, until the disappearance of the epoxy group, as indicated by chemical titration or nuclear magnetic resonance spectrometric analysis. Heating the mixture for from 2 to 40 hours usually suffices to complete the reaction, after which volatiles are removed by vacuum distillation.
  • the compounds of Formula II can then be acylated by reaction with an acylating agent, preferably an acyl halide, an acyl anhydride, or an isocyanate that contains polymerizable ethylenically unsaturated groups.
  • an acylating agent preferably an acyl halide, an acyl anhydride, or an isocyanate that contains polymerizable ethylenically unsaturated groups.
  • Preferred acylated compounds have the Formula: or
  • R, R 1 , R 3 , R 6 , R 7 , z, m and n are as def ined for
  • acylating agents include acid chlorides such as acetyl chloride, propionyl chloride, valeryl chloride, dodecanyl chloride, acrylolyl chloride, methacryloyl chloride, alpha-chloroacryloyl chloride, crotyl chloride, benzoyl chloride, phenylacetyl chloride,
  • 2,4-dichlorophenylacetyl chloride and the corresponding carboxylic acids and anhydrides; other anhydrides include the anhydrides of dicarboxylic acids such as maleic anhydride, succinic anhydride, methylenesuccinic anhydride, phthalic anhydride, and 3-chlorophthalic anhydride; and organic isocyanates such as methyl isocyanate, ethyl isocyanate, n-butyl isocyanate, phenyl isocyanate, 4-t-butyl isocyanate, acryloyloxyethyl isocyanate, methacryloyloxyethyl isocyanate,
  • the compounds of Formulas III and IV of the invention are prepared by addition of a suitable acylating agent to the compound II, e.g. an organic acid anhydride or halide or an organic isocyanate.
  • a suitable acylating agent e.g. an organic acid anhydride or halide or an organic isocyanate.
  • Suitable ethylenically unsaturated primary alcohols for use in the preparation of the compounds of the invention are the hydroxyalkyl acrylates having the formula: in which R 4 , R 5 , m and c are the same as defined for compounds of Formula I.
  • suitable hydroxyalkyl acrylates are the monoacrylate and monomethacrylate esters of aliphatic diols such as ethyleneglycol, propyleneglycol, butyleneglycol, hexamethyleneglycol, diethyleneglycol, and dimethylolcyclohexane; the diacrylates and dimethacrylates of aliphatic triols such as trimethylolmethane, 1,1,1-trimethylolpropane, 1,2,3-trimethylolpropane; the triacrylates and trimethacrylates of aliphatic tetrols such as pentaerythritol, 1,1,2,2-tetramethylolethane and 1,1,3,3-tetramethylopropane; the tetraacrylates and tetramethacrylates of polyols such as dipentaerythritol and 1,1,1,2,2-pentamethylolethane; and the pentaacrylates and pentamethacrylates of
  • Suitable ethylenically unsaturated primary alcohols for use in the preparation of the compounds of the invention are the hydroxyalkenes having the formula: in which R 4 , R 5 , m, d, b, and c are the same as defined for compounds of Formula I. Included among suitable hydroxyalkenes are allyl alcohol, methallyl alcohol, allyloxyethyl alcohol, 2-allyloxymethylpropanol (from dimethylolethane), and 2,2-di(allyloxymethyl)butanol (from trimethylolpropane).
  • Polymerization initiators suitable for use in the crosslinkable compositions of the invention are compounds which liberate or generate a free-radical on addition of energy.
  • Such initiators include peroxy, azo, and redox systems each of which are well known and are described frequently in polymerization art, e.g. Chapter II of Photochemistry, by Calvert and Pitts, John Wiley & Sons (1966). Included among free-radical initiators are the conventional heat activated catalysts such as organic peroxides and organic hydroperoxides; examples are benzoyl peroxide, tertiary-butyl perbenzoate, cumene hydroperoxide, azobis(isobutyronitrile) and the like.
  • the preferred catalysts are photopolymerization initiators which facilitate polymerization when the composition is irradiated.
  • acyloin and derivatives thereof such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and ⁇ -methylbenzoin; diketones such as benzil and diacetyl, etc.; organic sulfides such as diphenyl monosulfide, diphenyl disulfide, decyl phenyl sulfide, and tetramethylthiuram monosulfide; S-acyl dithiocarbamates, such as S-benzoyl-N,N-dimethyldithiocarbamate; phenones such as acetophenone, ⁇ , ⁇ , ⁇ -tribromacetophenone, ⁇ , ⁇ -diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, o-nitro- ⁇ , ⁇ , ⁇ -trib
  • the initiator is used in amounts ranging from about 0.01 to 5% by weight of the total polymerizable composition. When the quantity is less than 0 .01% by weight, the polymerization rate becomes extremely low. If the initiator is used in excess of 5% by weight, no correspondingly improved effect can be expected. Thus, addition of such greater quantity is economically unjustified. Preferably, about 0.25 to 1.0% of initiator is used in the polymerizable compositions.
  • the crosslinkable compositions of the invention are preferably diluted with an ethylenically unsaturated monomer.
  • Suitable ethylenically unsaturated monomers include methyl methacrylate, ethyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, styrene, 2-chlorostyrene, 2,4-dichlorostyrene, acrylic acid, acrylamide, acrylonitrile, t-butyl acrylate, methyl acrylate, butyl acrylate, 2-(N-butylcarbamyl)ethyl methacrylate and 2-(N-butylcarbamyl) ethyl methacrylate and 2-(N-ethylcarbamyl) ethyl methacrylate.
  • diluting monomers that can be incorporated into the composition of the invention include 1,4-butylene dimethacrylate or acrylate, ethylene dimethacrylate, hexanediol diacrylate or dimethacrylate, glyceryl diacrylate or methacrylate, glyceryl triacrylate or trimethacrylate, pentaerythritol triacrylate or trimethacrylate, pentaerythritol tetraacrylate or tetramethacrylate, diallyl phthalate, dipentaerythritol pentaacrylate, neopentylglycol triacrylate and 1,3,5-tri(2-methacryloxyethyl)-s-triazine.
  • compositions of the present invention may also contain compounds such as those disclosed in U.S. Patent No. 3,808,266:
  • R 20 is hydrogen or methyl
  • R 21 is hydrogen or methyl
  • n is 2 or 3
  • X' represents a divalent radical which is necessary for the completion of a five-or six-membered, unsubstitued or substituted, heterocyclic ring.
  • radical X' in the N-heterocyclic grouping of formula I can be, e.g., a radical of the formulae:
  • R 15 , R 16 , R 17 and R 18 can each inde pendent represent a hydrogen atom or an alkyl group, preferably a lower alkyl group having 1-4 carbon atoms, an alkenyl group, preferably a lower alkylene group having 1-4 carbon atoms, a cycloalkyl group (preferably of 3 to 8 carbon atoms), or an unsubstituted or substituted phenyl group.
  • the valence of the nitrogen atom on the last group may be satisfied by hydrogen, aliphatic, or aromatic groups R 19 , preferably of no more than eight carbon atoms, the aliphatic groups may be alkyl groups for example, and the cromatic group may be phenyl or alkylphenyl groups, for example.
  • the crosslinkable composition can also contain viscosity modifier or binder. Generally, up to about 50 percent by weight of a compatible polymer is used.
  • the polymer is an acrylic polymer such as poly(acrylic acid), a poly(methacrylic acid), poly(methyl methacrylate), poly(vinyl chloride), poly(vinyl acetate, poly (vinyl butyral) and the like.
  • compositions of the invention can also include a variety of addenda utilized for their known purpose, such as stabilizers, inhibitors, lubricants, flexibilizers, pigments, carbon black, dyes, reinforcing fillers such as finely divided silica, non-reinforcing fillers such as diatomaceous earth, metal oxides, asbestos, fiberglass, glass bubbles, talc, etc.
  • Fillers can generally be used in proportions up to about 200 percent by weight of the curable components but preferably are used up to about 50 percent by weight. Where the polymerizing energy is radiation, it is desirable that the addenda be transparent to the radiation.
  • compositions of the invention are prepared by simply mixing (under "safe light” conditions if the composition is to be sensitized to visible light) the polymerization catalyst and sensitizer (where used), the poly(ethylenically unsaturated alkoxyalkyl) heterocyclic compound, diluting monomers, binders and addenda.
  • Inert solvents may be employed if desired when effecting this mixture. Examples of suitable solvents are methanol, ethanol, acetone, acetonitrile and includes any solvent which does not react with the components of the mixture.
  • crosslinkable compositions of the invention can be used as adhesives, caulking and sealing compositions, casting and molding compositions, potting and encapsulating compositions, impregnating and coating compositions, etc., depending on the particular combination of components.
  • the polymerization catalyst is a photoinitiator
  • the composition can be a composition for in situ curing because of this insensitivity to oxygen.
  • the photopolymerizable compositions are particularly suitable for applications in the field of protective coatings and graphic arts because of their superior abrasion-resistance and adhesion to many rigid, resilient and flexible substrates such as metals, plastics, rubber, glass, paper, wood, and ceramics; their excellent resistance to most solvents and chemicals; their excellent flexibility and weatherability; and their capability for forming high resolution images.
  • water or water/alcohol developable resists for chemical milling, gravure images, offset plates, stencil making, screenless lithography, particulate binders as in microtaggants, relief printing plates, printed circuits, electron beam curing adhesives, radiation and protective coatings for glass, metal surfaces and the like and abrasion resistant coatings on a wide range of materials such as opthalmic lenses, light control films, and organic polymeric resin surfaces in general. Priming layers may be used if desired, and in some cases may be necessary.
  • the coatings of the present invention find application useful on substantially any solid substrate. Because the coatings of the present invention can be cured by radiation, even highly temperature sensitive substrates can be coated.
  • the substrates may be in substantially any form, such as sheets, films, fibers, fabrics and shaped solid objects.
  • polymeric resins including both thermoplastic and thermoset resins (e.g., polyesters, polyethers, polyamides, polyurethanes, polycarbonates, polyacrylates, polyolefins, polyvinyls cellulosesters, epoxy resins, polysiloxanes, etc.), ceramic substrates, including glass, fused ceramic sheetings, and fibers, metals and metallized surfaces, natural cellulosic materials, including wood and paper, natural resins, including rubber and gelatin and other various solid surfaces.
  • thermoplastic and thermoset resins e.g., polyesters, polyethers, polyamides, polyurethanes, polycarbonates, polyacrylates, polyolefins, polyvinyls cellulosesters, epoxy resins, polysiloxanes, etc.
  • ceramic substrates including glass, fused ceramic sheetings, and fibers, metals and metallized surfaces,
  • the coatings are useful particularly on refractive substrates (e.g., lenses, prisms and the like) as well as reflective substrates (street signs, mirrors, etc.). They are also useful on metallized polymeric film which is transparent and used as a light screen on windows.
  • refractive substrates e.g., lenses, prisms and the like
  • reflective substrates street signs, mirrors, etc.
  • metallized polymeric film which is transparent and used as a light screen on windows.
  • primer compositions comprising single ingredients or blends of materials, may be used to improve the bond of the coating to the substrate. Texturizing, chemical, or physical treatment of the surface may also be used to improve bonding.
  • the coatings of the invention are generally between 0.5 and 500 microns thick, preferably between 1 and 50 microns, and most preferably between 3 and 25 microns. Particularly useful substrates for application of the coatings of the present invention would be those requiring transparent protective coatings.
  • Finished photographic prints and films, paintings, transparencies, car windshields, painted surfaces, instant film (i.e., film which does not require external application of developing chemistry), photothermographic and thermographic paper and film, photoconductive substrates, opthalmic lenses, liquid crystal displays, motion picture film, street and traffic signs, reflective surfaces, retroreflective surfaces, traffic lights, and many other substrates are usefully coated according to the practice of the present invention. These coatings are particularly useful on optically functional surfaces or elements, particularly polarizing elements. These include both polymeric film type polarizers and the solvent-coated type polarizers such as are described in U.S. Patnets 2,400,877; 2,481,830; and 2,544,659.
  • the composition can be a composition for in situ curing because of this insensitivity to oxygen.
  • the photopolymerizable compositions are particularly suitable for applications in the field of protective coatings and graphic arts because of their superior abrasion-resistance and adhesion to many rigid, resilient and flexible substrates such as metals, metal oxides, plastics, rubber, glass, paper, wood, and ceramics; their excellent resistance to most solvents and chemicals; their excellent flexibility and weatherability; and their capability for forming high resolution images.
  • the photopolymerization of the compositions of the invention occurs on exposure of the compositions to any source of radiation emitting actinic radiation at a wavelength within the ultraviolet and visible spectral regions.
  • Suitable sources of radiation include mercury, xenon, carbon arc and tungsten filament lamps, sunlight, etc. Exposures may be from less than about 1 second to 10 minutes or more depending upon the amounts of the particular polymerizable materials and photopolymerization catalyst being utilized and depending upon the radiation source, distance from the source, and the thickness of the coating to be cured.
  • the compositions may also be polymerized by exposure to electron beam irradiation. Generally speaking, the dosage necessary is from less than 1 megarad to 100 megarad or more.
  • One of the major advantages with using electron beam curing is that highly pigmented compositions can be effectively cured at a faster rate than by mere exposure to actinic radiation.
  • the polymer layer should comprise the compounds of the present invention in order to obtain abrasion resistance.
  • Pentaerythritol triacrylate (44.3 g, 0.1 moles, hydroxyl equivalent weight of 443), .025 g 4-methoxyphenol, and 0.4 g borontrifluoride etherate were charged into a 250 ml three- necked round bottom flask equipped with mechanical stirrer, pressure equalizing dropping funnel, reflux condenser, and a CaS ⁇ 4 drying tube.
  • the chloroform was removed by vacuum distillation leaving as residue a viscous liquid that contains predominently compounds of the structure of Compound A.
  • Photocurable impurities introduced with the pentaerythritol triacrylate can be removed by trituration with diethyl ether.
  • a mixture of the liquid and 2% by weight of the photopolymerization initiator 2,2-dimethoxy-2- ⁇ henylacetophenone was coated onto 12 m polyester film and dried to provide a 2.5 m layer.
  • the layer was then cured in a UV Processor, Model No. CC 1202 N/A (manufactured by Radiation Polymer Co.) after one pass at 12 m/min. (40 feet/min.) under an 80 watts/cm (200 watts/inch) medium pressure mercury lamp.
  • the cured layer exhibited 95-100% cross-hatch adhesion, 2-7% Taber Haze, 13-16% haze in the Gardner Falling Sand Abrader (i.e., tested according to ASTM Designation Dl003-64( Procedure A)) and excellent resistance to abrasion by steel wool.
  • the layer was unaffected by treatment with ethanol, acetone, ethyl acetate, toluene, hexane, aqueous sodium hydroxide and 10% aqueous hydrochloric acid.
  • EXAMPLES 2-3 Preparation of 1,3-Bis[3-(2-acryloyloxyethoxy)-2-hydroxypropyl] -5,5-dimethyl-2,4-imidizolidinedione
  • Example 1 A layer of the compound containing 2% of 2,2-dimethoxy-2-phenylacetophenone was prepared and cured as in Example 1. The cured layer had chemical resistance similar to that of the layer of Example 1.
  • the analogous dimethacryloyl derivative (Compound C) was prepared in a similar manner utilizing 2-hydroxyethyl methacrylate in place of 2-hydroxyethyl acrylate. Layers prepared and cured with Compound C in the same manner as with Compound B had characteristics similar to those layers formed from Compound B.
  • Example 2 A layer of this material containing 2% of 2,2-dimethoxy-2-phenylacetophenone was prepared as in Example 1. This layer was cured to insolubility with a Hanovia 3D960 mercury arc lamp in 60 seconds. The sample was 6 cm from the light source.
  • the dried coating was 2.5 m thick.
  • EXAMPLE 11 A layer, 2.5 m in thickness, of Compound B containing 2% of the photopolymerization catalyst of Example 1 on 12 m polyester film was prepared as described in Example 1. A patterned template was placed over the layer and exposed in the UV Processor to one pass at 12 m/min. of an 80 watts/cm lamp. The exposed sheet was washed with cold water leaving an image having excellent resolution.
  • EXAMPLE 12 One part polyacrylic acid, one part compound A from Example 1, five parts water, five parts ethanol and 0.02 parts of the photopolymerization catalyst of Example 1 were mixed together to form a solution. A layer 5.0 m inm thickness of this solution was coated onto 12 m polyester as described in Example 1. A patterned templat was placed over the layer and exposed by a Hanovia 3D690 mercury arc lamp at a distance of 6 cm for two minutes. The exposed sheet was developed with cold water leaving a image having excellent resolution.
  • Example 2 A layer of this material containing 2% of the photopolymerization catalyst of Example 1 was prepared as in Example 1. This layer was cured to insolubility with a Hanovia 3D690 mercury arc lamp in 15 seconds. The sample was 6 cm from the light source.
  • Example 15 Into a 250 ml three-necked round bottom flask equipped with mechanical stirrer, pressure equalizing dropping funnel, reflux condenser, and calcium sulfate drying tube were charged 103.0 g pentaerythritol triacrylate (hydroxy equivalent weight of 515), 23.2 g 2-hydroxyethyl acrylate (0.2 moles), 0.08 g 4-methoxyphenol, and 1.0 g borontrifluoride etherate.
  • reaction flask was heated to 75°C and 55.2 g (0.40 molar epoxy equivalency) 1,3-bis(2,3-epoxypropyl)-5,5-dimethyl-2,4-imidizolidinedione in 20 ml chloroform was added dropwise over one hour. After the addition, the reaction flask temperature was raised to 88°C and stirred for 18.0 hours. At this time, titration of an aliquote for unreacted epoxide indicated the reaction was greater than 99% complete.
  • the volatiles were removed by vacuum distillation leaving a viscous liquid which contains a mixture of bis(triacryloyl)-, bis(monoacryloyl)-, and the unsymmetrical monoacryloyl-triacryloyl-imidizolidinedione, and impurities, introduced with the pentaerythritol triacrylate.
  • Example 16 Mixtures of compounds A - F (of Table 2) and 2% by weight of an appropriate photoinitiator were coated onto 12 m polyester and dried to provide a 2.5 m layer.
  • an appropriate photoinitiator for Compounds A through E, 2,2-dimethoxy-2-phenylacetophenone was used as a photoinitiator; for compound F benzophenone was used as a photoinitiator, as specified in USP 3925349.
  • the layers were then cured in a UV Processor, Model No. CC 1202 N/A (manufactured by Radiation Polymer Co.). An 80 watt/cm (200 watts/inch) medium pressure mercury arc lamp was used as the radiation source.
  • a film was considered cured when it displayed mar resistance after treatment with ethanol. All films were cured in one pass at a given belt speed unless indicated otherwise.
  • Compound F is described in USP 3925349 as photocurable in the presence of air. A film of this material cures at similar rates in the presence or absence of oxygen, but fails to display good mar resistance.
  • a solution containing 2.3g of compound A from Example 16, 2.3g acetone, and 0.033g diethoxyacetophenone was coated onto a 12 m polyethylene sheet with a #14 Meyer bar. The layer was dried and placed in a mounting for a Perkin Elmer Model No. 257 infrared spectrophotometer. The absorbances at 1630 cm -1 and 810 cm -1 , characteristic of acrylate unsaturation, were recorded. The mounting was removed from the spectrophotometer and passed through a UV processor as described in Example 16 at 50 ft/min. The mounting was returned to the spectrophotometer and the absorbances at 1630 cm -1 and 810 cm -1 were recorded and compared to the initial absorbances. This experiment showed that 70-80% of the acrylate functionality was consumed under the curing conditions. Five additional passes of this film at 50 ft/min in the UV processor failed to show any significant decrease in the acrylate infrared absorbances.
  • Example 18 One part polyacrylic acid, one part compound A from Example 1, five parts water, five parts ethanol and 0.02 parts of 2,2-dimethoxy-2- ⁇ henyl-acetophenone were mixed together to form a solution. A layer 5.0 m in thickness of this solution was coated onto 12 m polyester as described in Example 1. A patterned template was placed over the layer and exposed by a Hanovia 3D690 mercury arc lamp in air at a distance of 6 cm for two minutes. The exposed sheet was developed with cold water leaving an image having excellent resolution.
  • Examples 19-26 Coatings about 5 m thick were prepared by coating using a #20 Meyer bar onto about 12 m polyethylene film primed with polyvinylidene chloride 50% solutions in ethyl acetate (other solvents such as ketones and lower alcohols are equally suitable) and drying mixtures of Compound A of Example 1, zero to 100% of Compound 2 of Example 1, and pentaerythritol triacrylate (PTA) based on total weight of Compounds A, B and PTA.
  • ethyl acetate other solvents such as ketones and lower alcohols are equally suitable
  • Table 3 shows that coatings prepared from the hexaacryloyloxyhydantoin, Compound A, and up to more than 50% of the diacryloyloxyhydantoin, Compound B, have excellent resistance to abrasion as measured by Taber, falling sand and steel wool procedures. At up to about 30% Compound B, abrasion resistance is superior. When coatings were prepared as for Examples 3-10 but using photoinitiator concentrations from 0.4 to 3% and tested, similar abrasion resistance and cross-hatch adhesion was obtained.

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  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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PCT/US1980/000612 1979-06-25 1980-05-22 Poly(ethylenically unsaturated alkoxy)heterocyclic compounds and crosslinked polymeric coatings WO1981000011A1 (en)

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BR8008725A BR8008725A (pt) 1979-06-25 1980-05-22 Compostos heterociclicos de poli-(alcoxi etilenicamente insaturado)
DE8080901348T DE3069342D1 (en) 1979-06-25 1980-05-22 Poly(ethylenically unsaturated alkoxy)heterocyclic compounds and crosslinked polymeric coatings

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US06/051,877 US4262072A (en) 1979-06-25 1979-06-25 Poly(ethylenically unsaturated alkoxy) heterocyclic protective coatings
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US06/051,876 US4249011A (en) 1979-06-25 1979-06-25 Poly(ethylenically unsaturated alkoxy) heterocyclic compounds

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US4526139A (en) * 1983-09-09 1985-07-02 Medlinsky Edward I Internal combustion engine
WO1993025623A1 (en) * 1992-06-08 1993-12-23 Minnesota Mining And Manufacturing Company Abrasion-resistant coating composition and abrasion resistant energy control sheet
US9720155B2 (en) 2014-05-02 2017-08-01 Sabic Global Technologies Multilayered articles with low optical retardation

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DE4436192C1 (de) * 1994-10-11 1996-03-21 Kurz Leonhard Fa Strukturanordnung, insbesondere für ein Sicherheitselement

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4526139A (en) * 1983-09-09 1985-07-02 Medlinsky Edward I Internal combustion engine
WO1993025623A1 (en) * 1992-06-08 1993-12-23 Minnesota Mining And Manufacturing Company Abrasion-resistant coating composition and abrasion resistant energy control sheet
US9720155B2 (en) 2014-05-02 2017-08-01 Sabic Global Technologies Multilayered articles with low optical retardation

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EP0030969B1 (en) 1984-10-03
AU543067B2 (en) 1985-03-28
MX155302A (es) 1988-02-16
IT8049059A0 (it) 1980-06-24
JPH0348183B2 (en, 2012) 1991-07-23
DE3069342D1 (en) 1984-11-08
EP0030969A1 (en) 1981-07-01
IT1145342B (it) 1986-11-05
CH664060GA3 (en, 2012) 1988-02-15
JPS56500743A (en, 2012) 1981-06-04
AU6126180A (en) 1981-01-14
EP0030969A4 (en) 1981-10-27
BR8008725A (pt) 1981-04-28

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