WO1995000573A1 - Polymeres reactifs a chaines laterales souples rattachees a une extremite, prepares a partir d'isocyanates ethyleniquement insatures - Google Patents

Polymeres reactifs a chaines laterales souples rattachees a une extremite, prepares a partir d'isocyanates ethyleniquement insatures Download PDF

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Publication number
WO1995000573A1
WO1995000573A1 PCT/US1994/006990 US9406990W WO9500573A1 WO 1995000573 A1 WO1995000573 A1 WO 1995000573A1 US 9406990 W US9406990 W US 9406990W WO 9500573 A1 WO9500573 A1 WO 9500573A1
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Prior art keywords
polymer
ethylenically unsaturated
vinyl
polymers
side chains
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PCT/US1994/006990
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English (en)
Inventor
James Wayne Taylor
Martha Jean Collins
David Robinson Bassett
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Union Carbide Chemicals & Plastics
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Priority to AU73151/94A priority Critical patent/AU7315194A/en
Publication of WO1995000573A1 publication Critical patent/WO1995000573A1/fr

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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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C08G18/6233—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols the monomers or polymers being esterified with carboxylic acids or lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/80—Compositions for aqueous adhesives

Definitions

  • This invention relates to reactive polymers, e.g., aqueous emulsion polymers, having pendant flexible or dangling side chains prepared from ethylenically unsaturated isocyanates.
  • the reactive polymers contain ethylenic unsaturation near the surface or in the surface area of the particles that form the polymers, the ethylenic unsaturation being connected to the polymer through the pendant flexible or dangling side chains.
  • This invention also relates to the process for preparing the reactive polymers, to crosslinkable
  • the reactive polymers are useful as decorative and functional coatings, inks, adhesives, textile coatings and sealants.
  • Aqueous emulsion polymers or latexes in both clear and pigmented form are well-known, widely-used articles of commerce. Examples of these uses include interior and exterior architectural coatings, general metal coatings, adhesives, and the like.
  • the latexes are formed by aqueous emulsion polymerization of monoethylenically unsaturated monomers as styrene, butyl acrylate, methyl
  • a core and shell latex in which the core of the particles has a given composition that may contain a small amount of the functional groups or be devoid of them and the shell or outer layers of the particle have a different composition which may be rich in the functional groups, and the like.
  • This invention relates in part to a polymer having one or more pendant flexible side chains connected thereto, wherein said pendant flexible side chains contain ethylenic unsaturation and are connected to said polymer by a urethane linkage, said urethane linkage formed by the reaction of an ethylenically unsaturated isocyanate with a hydroxyl group on said polymer.
  • This invention also relates in part to a process for preparing a polymer having one or more pendant flexible side chains connected thereto comprising: (a) preparing a precursor polymer having hydroxyl group functionality from one or more ethylenically
  • step (c) optionally recovering the step (b) polymer and redissolving it in an organic solvent.
  • ethylenic unsaturation of various types can be formed on, in, or near the surface of polymer particles that contain free, reactive hydroxyl functionality by first preparing a precursor polymer and then post reacting it with one or more suitable ethylenically unsaturated isocyanates containing a functional group that will react with all or a portion of the free, reactive hydroxyl functionality on the precursor polymer particle.
  • the post reactant will contain an ethylenic unsaturation group that can air dry or force dry into a crosslinked, solvent resistant coating with broad utility characteristics. Air dry means to cure the liquid coating into a solid film by allowing it to remain under ambient conditions for a period of time sufficient to effect solidification.
  • ethylenic unsaturation shall include all permissible compounds, groups or substituents having at least one carbon-carbon double bond including, for example, (meth)acrylates, vinyls, allyls, alkenes and the like.
  • the post modified polymer containing ethylenic unsaturation is recovered from the aqueous environment, dissolved in an organic solvent, and applied to a substrate to effect air-cure crosslinking.
  • the water-borne polymer particles can be crosslinked with free radicals generated from an actinic energy source such as an electron beam or by formulation with a free radical-generating photoinitiator and, if necessary, a synergist, and exposed to an ultraviolet light source such as sunlight, mercury vapor lamps, xenon lamps, etc.
  • the polymer precursor containing free, reactive hydroxyl functionality can be recovered from the aqueous media and dissolved in an organic solvent or can be prepared in an organic solvent.
  • the polymer in organic solvent can be modified by post reaction with one or more of the above described reactants for aqueous systems to form a polymer with pendant flexible chains having ethylenic unsaturation connected thereto that can be crosslinked under ambient, air-cure conditions or radiation-cure conditions.
  • the post modified polymers containing ethylenic unsaturation neat or formulated with photoinitiator and/or other radiation-reactive chemicals is recovered as a solid, uncrosslinked film by removal of either the aqueous or organic solvent media.
  • the solid film is then used as a photoresist in the manufacture of printed circuit boards or other article by selective exposure to radiation. Selective exposure is provided by a mask through which radiation does not penetrate.
  • the reactive polymers of the invention can be used in a variety of ways including but not limited to clear, colored, filled, or pigmented crosslinked latexes, water-borne alkyds, solvent-borne alkyds, radiation curable systems, and the like.
  • Illustrative of generalized utility areas are coatings for metal, paper, plastics, wood, and masonry; inks; adhesives; binding agents for concrete;
  • photoresists and the like.
  • specific coating end uses that can be mentioned are interior and exterior architectural coatings, can coatings, office and home furniture coatings, pipeline coatings, sign coatings, maintenance coatings, business machine coatings, functional and decorative automotive coatings, textile coatings, conformal coatings, electrical and electronic coatings and the like.
  • Hydroxyl group functionalized polymer particles can be reacted with one or more ethylenically unsaturated isocyanates, in which the reaction takes place with a hydroxyl group to form a free ethylenically unsaturated terminated, pendant flexible side chain connected to the polymer particle through a urethane linkage.
  • urethane linkage is
  • the polymers having hydroxyl functionality can be prepared from a variety of monoethylenically unsaturated monomers including, for example, acrylates and methacrylates (both referred to herein as (meth)acrylates); vinyl esters; vinyl aromatic, cycloaliphatic, and heterocycles; hydroxyalkyl (meth)acrylates and their derivatives; vinyl halogens and vinylidine halogens; alkenes and substituted alkenes; nitriles; and vinyl ethers.
  • monoethylenically unsaturated monomers including, for example, acrylates and methacrylates (both referred to herein as (meth)acrylates); vinyl esters; vinyl aromatic, cycloaliphatic, and heterocycles; hydroxyalkyl (meth)acrylates and their derivatives; vinyl halogens and vinylidine halogens; alkenes and substituted alkenes; nitriles; and vinyl ethers.
  • (meth)acrylates are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylates, butyl (meth)acrylates, pentyl (meth)acrylates, hexyl (meth)acrylates, heptyl (meth)acrylates, octyl (meth)acrylates, nonyl (meth)acrylates, decyl (meth)acrylates, (meth)acrylic acid, and the like
  • vinyl esters are vinyl acetate, vinyl propionates, vinyl butyrates, vinyl pivalates, vinyl hexanoates, vinyl hepanoates, vinyl octanoates, vinyl isovalerate, vinyl 2-ethoxymethylsulfate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylates, butyl (meth)acrylates, pentyl (meth)acrylates, hexyl
  • vinyl aromatic, cycloaliphatic, and heterocycles are styrene, vinyl cyclohexane, vinyl cyclopentane, vinyl toluene, vinyl anthracenes, 3-vinyl benzyl chloride, 4-vinyl biphenyl, 4-vinyl-1-cyclohexene, vinyl cyclooctane, 2-vinyl naphthalene, 5-vinyl-2-norbornene, 1-vinyl imidazole, 2-vinyl pyridine, 4-vinyl pyridine, 1-vinyl-2-pyrrolidinone, 9-vinyl carbazole, 3-vinylbenzyl chloride, and the like.
  • the hydroxyalkyl (meth)acrylates and their derivatives include 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), ethylene oxide and propylene derivatives of HEA and HPA containing from 1 to about 20 moles of the alkylene oxide, caprolactone (meth)acrylates which are epsilon-caprolactone derivatives of HEA and HPA containing from 1 to about 6 moles of epsilon-caprolactone, carboxylic acid terminated adducts of HEA and HPA and the alkylene oxide and caprolactone derivatives of HEA and HPA, and the like,
  • Illustrative of the vinyl halogens and vinyhdine halogens are vinyl chloride, vinylidine chloride, vinyl fluoride, vinyhdine fluoride, and the like.
  • alkenes and substituted alkenes are ethylene, propylene, butenes, pentenes, hexenes, heptenes, octenes, nonenes, decenes, 4-chloro-1-butene, 4, 6-dichloro-1-hexene, 5-fluoro-2-hexene, and the like.
  • nitriles are acrylonitrile, methacrylonitrile, and the like
  • vinyl ethers are methyl vinyl ether, ethyl vinyl ether, propyl vinyl ethers, butyl vinyl ethers, pentyl vinyl ethers, hexyl vinyl ethers, hepty vinyl ethers, octyl vinyl ethers, 2-methyl-1-butyl vinyl ether, and the like.
  • carboxylic acid monomers can be used, such as acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, crotonic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, maleic acid and the like including mixtures thereof.
  • the polymers are prepared by conventional techniques as exemplified herein and as are known to those skilled in the art of polymerization.
  • the molecular weight of the copolymers making up the polymer particles can vary over wide ranges of average molecular weight and can have number-average molecular weights of from about 1000 to about 1,000,000 or more with a distribution of molecular weights existing.
  • the polymer particles of this invention contain a major quantity of the functional groups in, at or near the surface (i.e., the surface region) of the particles, though it is realized that some of the functional groups may be positioned within the interior of the particles.
  • the number of copolymers in each polymer particle is indeterminate since particle size and copolymer molecular weight will vary, it is important that, on the average, hydroxyl functionality exist on a majority of any copolymer molecules and that at least some of the functionality be found in the surface region or related region so it can react with the post reaction reactants.
  • Other functional groups such as carboxyl, amine, etc., may also be present in the hydroxyl functional polymers, i.e., precursor polymers, used in this invention,
  • Illustrative of the ethylenically unsaturated isocyanates that can be used to react with the precursor polymer particles to produce the reactive polymers of this invention are the isocyanato alkyl (meth)acrylates such as 2-isocyanatoethyl methacrylate, 3-isocyanatopropyl methacrylate, and the like; the monoisocyanates prepared from diolefins such as the dialkylidene aryls that produce compounds such as 1-(1-isocyanato-1-methyl ethyl)-3-(1-methyl ethenyl) benzene (p-TMI), 1-(1-isocyanato-1-methyl ethyl)-4-(1-methyl ethenyl) benzene (m-TMI), 1-(1-isocyanato-1-methyl propyl)-3-(1-methyl propenyl) benzene, 1-(1-isocyanato-1-methyl propyl)-4
  • isocyanates may be used for purposes of this invention. Both
  • initial aqueous emulsions used to prepare the aqueous emulsion polymers of this invention have an initial pH of about 2.0 to 10.5 and contain about 0.05 to 20% or more of hydroxyl functionality, preferably an initial pH of 3.5 to 9.0 and contain from about 0.1% to 15% hydroxyl functionality, and are prepared at about 40°C to about 100°C for about 6 to 48 hours, preferably at about 60°C to about 90°C for about 10 to about 24 hours under atmospheric pressure or superatmospheric pressure of about 15 psig to about 100 psig.
  • the post reaction leading to the reactive polymers of this invention are carried out at a temperature of from about 0°C to about 100°C, preferably from about 20°C to about 90°C, for about 30 minutes to 24 hours or more under atmospheric or superatmospheric pressure of about 15 psig to about 100 psig.
  • a stoichiometric deficiency of the ethylenically unsaturated isocyanate may be employed in order to leave some hydroxyl functionality in the polymer. Excess isocyanate is generally avoided since it introduces residual unpolymerized monomer which is undesirable. At least about 0.5% of the ethylenically unsatured isocyanate, based on the weight of the polymer, is used. Based on the hydroxyl content of the precursor polymer, it is preferred to consume at least 5%, preferably from 10% to about 90%, of the hydroxyl functionality by reaction with the ethylenically unsaturated isocyanate.
  • hydroxyl functional polymers i.e., precursor polymers, used in this invention.
  • Other permissible post reactions may be carried out in a sequential manner so there is no adverse interaction of the reactants used for the post reaction of this invention.
  • Illustrative of other such post reactions include, for example, (1) reaction with a carbodiimide (meth)acrylate wherein reaction takes place with carboxyl groups on the precursor polymer particle; (2) reaction with an imine to form amine groups on the precursor polymer particle and then with an ethylenically unsaturated isocyanate wherein reaction takes place with the amine groups to form free vinyl groups connected to the particle with urea linkages; (3) reaction with an imine to form amine groups on the precursor polymer particle and then with either a mixture or a sequence of glycidyl (meth)acrylate and a carbodiimide (meth)acrylate; and the like. Both substituted and unsubstituted post reactants may be used for purposes of this invention.
  • Suitable other post reactions which may be employed herein include those disclosed in U.S. Patent Application Serial No. (D-16967), U.S. Patent Application Serial No. (D-16894) and U.S. Patent Application Serial No. (D-17136), all of which are incorporated herein by reference. This invention is not intended to be limited in any manner by the number or combination of permissible post reactions.
  • the reactive polymers e.g., aqueous emulsion polymers, of this invention can be used in a variety of ways illustrative of which are as air-dry coatings that will increase in molecular weight
  • the reactive polymers of this invention may be used alone or in combination with other systems illustrative of which are aqueous emulsions, water redurible alkyds, solutions of polymers, radiation-curable (meth)acrylates or epoxides, unsaturated fatty acid derivatives, linseed oil, soybean oil, tall oil, and the like.
  • aqueous alkyds having molecular weights of from about 500 to 5000 are prepared by adding chain transfer agents to the emulsion polymers during polymerization.
  • the reactive polymers of this invention are recovered as a solid, redissolved in an organic solvent, and formulated into solvent-borne coatings, particularly high solids alkyd coatings when low molecular weight polymers are formed in the emulsion process.
  • Suitable solvents are polar in nature illustrative of which are esters, ketones, esters of lactic acid; ethylene oxide glycol ethers as ethylene glycol monomethyl ether, ethylene glycol and diethylene glycol monoethyl ethers, ethylene glycol and diethylene glycol monopropyl ethers, ethylene glycol and diethylene glycol monobutyl ethers, and ethylene glycol and diethylene glycol monohexyl ethers; propylene oxide glycol ethers such as propylene glycol and dipropylene glycol monomethyl ethers, propylene glycol and dipropylene glycol
  • plasticizers When polymers with glass transition temperatures greater than room temperature are formed, film forming agents or plasticizers of various types may be incorporated into the formulations.
  • plasticizers may be (1) of a nonreactive nature, illustrative of which are the various esters, ketones, hydroxyethers, and the like which may be fugitive in nature when they have low molecular weight and are lost via evaporation or may be retained by the dry film when they have relatively high molecular weight; (2) of a reactive nature and contain ethylenic unsaturation which reacts with the unsaturation in the polymers of the invention and thus become incorporated into the final film, illustrative of which are diethylene glycol diacrylate, ethylene glycol diacrylate, divinyl adipate, disiopropenyl adipate, divinyl succinate, vinyl crotonate, diallyl phthalate, urethane acrylates, acrylated epoxides, timethylol propane triacrylate
  • Optional heavy metal driers that may be incorporated into the coatings to promote curing.
  • These driers are metal salts of organic acids illustrative of which acids are tall oil fatty acids, ethylhexanoic acid, neodecanoic acids, naphthenic acids, and the like.
  • Illustrative of typical metals used for air- or ambient-dry systems are cobalt, zirconium, and manganese, and the like, and for heat-cure coatings are iron, manganese, cobalt, cerium, and the like.
  • Auxiliary driers include lead, barium, calcium, zirconyl (ZrO-) , zinc, and the like. If desired, mixtures of the various driers can be used.
  • Illustrative of the peroxides or compounds that will generate oxygen when heated that can be used in the thermally curable coating compositions of this invention are benzoyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxide, and the like. These compounds are used in an amount of about 0.05% to about 5%, preferably from about 0.1% to about 2.5%. It is known to those skilled in the art of these compounds that the cure temperature and
  • decomposition temperature of any chosen compound must be properly considered when they are used.
  • photoinitiators used in the photocurable coating compositions are 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetopheneone, 1-hydroxycyclohexylphenyl ketone, acetophenone, and the like.
  • hydrogen abstraction-type photoinitiators are benzophenone, benzophenone derivatives, 2-chlorothioxanthone, isopropylthioxanthone, fluorenone, benzil, 9,10-anthraquinone, camphor quinones, 1,3,5-triacetylbenzene, 3-ketocoumarines, acridone, bis-(4,4'-dimethylamino)benzophenone, and the like.
  • amine, amides, urethanes or ureas with a hydrogen-bearing carbon atom in the alpha position to the nitrogen group among which one can mention dimethylethanol amine, triethyl amine; primary, secondary, and tertiary amine-terminated
  • polypropylene oxide polyols as well urea and urethane derivatives of such polyols, and the like.
  • the reactive polymers of this invention can be cured alone with or without added photoinitiator when exposed to ultraviolet light, they may be combined with one or more other radiation-polymerizable ethylenically unsaturated compounds such as substituted or unsubstituted (meth)acrylates.
  • Illustrative of the (meth)acrylates suitable for use in the radiation curable compositions of the invention are the esters of (meth)acrylic acid with monohydric and polyhydric compounds among which one can mention ethyl, butyl, hexyl, octyl, decyl, and the like (meth)acrylates; neopentyl
  • (meth)acrylate trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate and tetra(meth)crylate
  • caprolactone (meth)acrylates which are adducts of 1 to 10 moles of epsilon-caprolactone and a hydroxylalkyl (meth)acrylate, alkoxylated (meth)acrylates, glycerol (meth)acrylates, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate di(meth)acrylate, isobornyl (meth)acrylate, tripropylene glycol di(meth)acrylate, unsaturated polyesters, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate
  • di(meth)acrylates di(meth)acrylates, urethane (meth)acrylates, (meth)acrylated epoxides, (meth)acrylated linseed oil, (meth)acrylated soybean oil,
  • formulations may contain N-vinyl pyrrolidone, divinylbenzene, and the like.
  • the reactive polymers e.g., aqueous emulsions, of this invention can be formulated with a variety of vinyl esters alone or in combination with other radiation-polymerizable ethylenically-unsaturated compounds in the photocurable compositions of this invention.
  • the vinyl esters are vinyl 2-ethylhexanoate, vinyl benzoate, vinyl isovalerate, vinyl nonylates, vinyl neononanoate, vinyl neodecanoate, vinyl myristate, vinyl oleate, vinyl linoleate, vinyl abietate, divinyl adipate, divinyl oxalate.
  • divinyl succinate divinyl fumarate, divinyl maleate, diisopropenyl adipate, trivinyl mellitate, trivinyl citrate, 1, 2, 4-trivinyl benzenetricarboxylate, tetravinyl mellophanate, 3,3',4,4'-tetravinyl benzophenonetetracarboxylate, and the like.
  • vinyl ester can also be used as reactive
  • the photopolymerization is carried out by exposing the uncured film or coating to light radiation which is rich in short wave radiation.
  • light radiation which is rich in short wave radiation.
  • Particularly useful is radiation of about 200 to 450 nanometers in wavelength
  • Illustrative of appropriate light sources are low-pressure, medium pressure, and high-pressure mercury vapor lamps as well as lamps of this type that have been doped to exclude selected wavelengths; xenon and other flash-type lamps; lasers operating in the above listed wavelength range; sunlight, and the like.
  • Other sources of radiant energy such as electron beams, gamma radiation, X-rays, and so on can also be used.
  • any permissible conventional additives, processing aids, etc. may be employed in conventional amounts in the compositions and processes of this invention. This invention is not intended to be limited in any manner by any permissible additives, processing aids, and the like .
  • the coating compositions of the invention are applied to appropriate substrates as thin films by a variety of processes illustrative of which are roll coating, dip coating, spray coating, brushing, flexographic, lithographic, and offset-web printing processes, and the like.
  • the term "substituted" is contemplated to include all permissible substituents of organic compounds unless otherwise indicated.
  • the permissible substituents include acyclic and cyclic, branched and unhranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds.
  • Illustrative substituents include, for example, alkyl, alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl, halogen and the like in which the number of carbons can range from 1 to about 20 or more, preferably from 1 to about 12.
  • the permissible substitutents can be one or more and the same or different for appropriate organic compounds. This invention is not intended to be limited in any manner by the permissible substituents of organic compounds.
  • the gel fraction or gel content is the amount of material that is insoluble when a given mass of the cured coating is extracted with tetrahydrofuran (THF) for 18 hours at room temperature.
  • THF tetrahydrofuran
  • the extracted film is removed from the THF, rinsed with fresh THF, and dried at 110°C for one hour.
  • the gel fraction, expressed as a percentage, is calculated with the following expression.
  • DOI - - measurement of the light image reflected off a surface using a commercially available DOI instrument
  • Surfactant 1 A sodium dioctyl sulfosuccinate anionic surfactant commercially available from American Cyanamid Company under the designation Aerosol ® OT-75.
  • Surfactant 2 A 70% solution of nonyl phenol-based alkylene oxide nonionic surfactant in water commercially available from Union Carbide Chemicals and Plastics Company Inc. under the designation Tergitol® NP-40.
  • a glass resin kettle equipped for temperature control and agitation was charged with 1,100.0 grams of deionized water, 0.34 gram of Surfactant 1, 1.30 grams of Surfactant 2, and 50 grams of the monomer solution.
  • a nitrogen purge was started in the reaction mixture, and the contents of the resin kettle were increased to 85°C at which point an initiator mixture consisting of 5.6 grams of ammonium persulfate dissolved in 147 grams of deionized water were added to the kettle and the temperature was set and maintained at 80°C. The remainder of the monomer solution was then fed to the reactor over a period of 225 minutes.
  • an initiator feed composed of 4.2 grams of ammonium persulfate dissolved in 107.8 grams of deionized water was started and fed to the reactor over a time period of 240 minutes.
  • a post initiator solution composed of 0.3 gram of ammonium persulfate and 0.3 gram of sodium metabisulfite dissolved in 49.4 grams of water was added over a time period of 30 minutes.
  • the aqueous emulsion of polymer was kept at the 80°C reaction
  • the aqueous emulsion polymer was prepared in the same manner as that used for Preparation A. There was a 100% conversion of monomer, polymer or solids content was 43%.
  • the aqueous emulsion was maintained at 80°C for 15 minutes after the addition, cooled to room temperature, and 20 grams of Surfactant 2 were added, stirred for an additional 15 minutes, and then filtered. A total of 2146 grams of emulsion was obtained with a solids content of 46%.
  • the copolymer had a number-average molecular weight of 73,500 and a weight-average molecular weight of 467,000 as measured by gel permeation chromatograph using polystyrene standards.
  • Example 3 The same equipment, procedure, and ingredients of Example 3 were used except 39.1 grams of 1-(1-isocyanato-1-methyl ethyl)-4-(1-methyl ethenyl) benzene, m-TMI were used. After 5.5 hours at 80°C, infrared analysis indicated 6.2% of the TMI remained.
  • Foamaster® VL (Henkel) were added while stirring, and then filtered. A total of 797 grams of the aqueous emulsion polymer, 49.35% solids, was obtained.
  • Example 3 polymer 6.31 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
  • Example 4 polymer - - - - - 6.31 6.31 6.31 6.31 6.31 6.31 6.31 6.31 6.31 6.31 6.31 6.31
  • the pigment grind materials are conventional materials and commercially available as follows: Tamol® 681 (Rohm & Haas); AMP-95 (Angus Chemical); Triton® X-102 (Union Carbide Chemicals and Plastics Company Inc.); DeeFo® 495 (Ultra Additives); Ti-Pure® R-900 (DuPont); and Nuosept® 95 (Huls).
  • Tamol® 681 Rohm & Haas
  • AMP-95 Angus Chemical
  • Triton® X-102 Union Carbide Chemicals and Plastics Company Inc.
  • DeeFo® 495 Ultra Additives
  • Ti-Pure® R-900 DuPont
  • Nuosept® 95 Huls
  • Titanium Dioxide Ti-Pure® R-900 250.00
  • the paint was prepared from the pigment grind by blending the following ingredients in what is termed in the art as a letdown procedure.
  • the letdown ingredients are conventional materials and are commercially available as follows: Triton® Gr-7M (Union Carbide Chemicals and Plastics Company Inc.); DeeFo® 495 (Ultra Additives); and Acrysol® SCT-275 (Rohm & Haas). Table 8
  • Example 3 or Example 4* 480.00
  • Example 14 When the aqueous emulsion of Preparation C was used, Control IX resulted; when the modified aqueous emulsion of Example 3 was used, Example 13 resulted; and when the modified aqueous emulsion of Example 4 was used, Example 14 resulted.
  • a seven-mil wet film of a commercial gloss alkyl paint (Glidden Alkyd Enamel 4554 green) was made on a Leneta scrub panel by the draw-down technique.
  • the alkyd film was allowed to air dry for more than two days.
  • a seven-mil wet draw down of the Control IX, Example 13, or Example 14 paint was drawdown over the aged commercial alkyd and allowed to air dry for three days.
  • the dried or cured test control or example paint was cross hatched with a razor blade and submerged into water for 30 minutes. While the paint was still wet, the panel was placed on a Gardner scrub machine.
  • a glass reactor equipped with a stirrer, thermometer, nitrogen inlet and outlet, and feeding ports was charged with 986.43 grams of deionized water, 1.07 grams of Surfactant 1, and 1.43 grams of Surfactant 2.
  • a nitrogen purge was started, and the contents of the reactor were heated to 80° C while stirring at 400 revolutions per minute (rpm).
  • 50 grams of Feed 1, Table 10 were added along with a mixture containing 3.0 grams of potassium persulfate dissolved in 147 grams of deionized water and stirred for 5 minutes.
  • Total time of addition for Feeds 1 and 2 was 240 minutes. After the reactants were added to the reactor, the aqueous emulsion was heated for 15 minutes at 80° C. The emulsion, which had a 42.9% total solids, was cooled and stored for future use.
  • a glass reactor was equipped with a condenser, stirrer, and thermometer and charged with 400 grams of Preparation D emulsion. Then a mixture containing 1.00 gram allyl glycidyl ether, 10.11 grams of 1-(1-isocyanato-1-mehyl ethyl)-3-(1-methyl
  • ethenyl)benzene m-TMI
  • Surfactant 1 0.055 gram Surfactant 1 were added in a dropwise manner to the stirring emulsion at room temperature. Then 10.1 grams of deionized water were added to adjust solids. The emulsion was stirred for 30 minutes at room temperature and then heated to 80°C and held there for 3 hours. The latex was cooled to room temperature and stored for future use. Total solids content was 43.2%. The latex gel fraction was 37.8%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention se rapporte à des polymères réactifs, tels que des polymères en émulsion aqueuse, comprenant des chaînes latérales souples rattachés à une extrémité, et préparés à partir d'isocyanates éthyléniquement insaturés. Ces polymères réactifs présentent une insaturation éthylénique à proximité de la surface ou dans la surface des particules formant les polymères, l'insaturation éthylénique étant reliée au polymère par des chaînes latérales souples suspendues ou rattachées à une extrémité. Cette invention se rapporte également au procédé de préparation de ces polymères réactifs, à des formulations réticulables basées sur ces polymères réactifs, ainsi qu'à des films thermoplastiques et réticulés préparés à partir de ces derniers. Ces polymères réactifs peuvent être utilisés comme revêtements décoratifs ou fonctionnels, encres, adhésifs, apprêts de tissus et matières d'étanchéité.
PCT/US1994/006990 1993-06-23 1994-06-20 Polymeres reactifs a chaines laterales souples rattachees a une extremite, prepares a partir d'isocyanates ethyleniquement insatures WO1995000573A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU73151/94A AU7315194A (en) 1993-06-23 1994-06-20 Reactive polymers having pendant flexible side chains prepared from ethylenically unsaturated isocyanates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US8205793A 1993-06-23 1993-06-23
US082,057 1993-06-23

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WO1995000573A1 true WO1995000573A1 (fr) 1995-01-05

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5891950A (en) * 1996-05-28 1999-04-06 Eastman Chemical Company Use of stable amino-functional latexes in water-based inks
EP0608891B1 (fr) * 1993-01-28 1999-09-22 National Starch and Chemical Investment Holding Corporation Adhésifs thermofusibles sensibles à la pression durcissables par irradiation
US5962556A (en) * 1996-10-22 1999-10-05 Eastman Chemical Company Functional latexes resistant to hydrolysis
US5998543A (en) * 1996-05-28 1999-12-07 Eastman Chemical Company Stable amino-containing polymer latex blends
EP0977085A1 (fr) * 1998-07-31 2000-02-02 Dai Nippon Printing Co., Ltd. Composition photosensible à base de résine et filtre couleur
US6028155A (en) * 1997-05-21 2000-02-22 Eastman Chemical Company Surfactant-containing acetoacetoxy-functional and enamine-functional polymers
US6060556A (en) * 1997-05-21 2000-05-09 Eastman Chemical Company Process for preparing reactive latex blends which are chemically and physically stable until film formation
EP1035439A2 (fr) * 1999-02-25 2000-09-13 Dai Nippon Printing Co., Ltd. Composition photosensible, filtre coloré et résine copolymère destinée à ceux-ci
EP1076070A2 (fr) * 1999-08-11 2001-02-14 Dai Nippon Printing Co., Ltd. Résine stable, composition de résine durcissable, procédé pour la préparation, filtre couleur et panneau à cristal liquide
WO2001027182A1 (fr) * 1999-10-08 2001-04-19 Dai Nippon Printing Co., Ltd. Resine durcissable a photosensibilite elevee, composition de resine photodurcissable, procede de production correspondant, filtre couleur et panneau d'affichage a cristaux liquides
EP1429184A1 (fr) * 2002-12-12 2004-06-16 Shipley Company, L.L.C. Copolymère fonctionnalisé pour composition photopolymérisable
WO2005103822A2 (fr) * 2004-04-22 2005-11-03 Showa Denko K.K. Composition de résine photosensible, produit vulcanise a partir de celle-ci et procédé de fabrication de carte à circuit imprimé utilisant ledit produit
US8546485B2 (en) 2010-12-20 2013-10-01 Henkel Corporation Photocurable dicing die bonding tape
CN113801294A (zh) * 2021-08-10 2021-12-17 华南理工大学 一种高强度和宽温域高阻尼聚氨酯弹性体材料及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2134645A1 (fr) * 1971-04-30 1972-12-08 Agfa Gevaert Ag
FR2136779A5 (fr) * 1971-04-30 1972-12-22 Bayer Ag
EP0206158A2 (fr) * 1985-06-24 1986-12-30 Siemens Aktiengesellschaft Photopolymères à base de polyéther
EP0259726A2 (fr) * 1986-09-11 1988-03-16 Siemens Aktiengesellschaft Photopolymères à base d'époxyde
US5049623A (en) * 1989-08-03 1991-09-17 Monsanto Company Ethylenically unsaturated carbamates and coating compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2134645A1 (fr) * 1971-04-30 1972-12-08 Agfa Gevaert Ag
FR2136779A5 (fr) * 1971-04-30 1972-12-22 Bayer Ag
EP0206158A2 (fr) * 1985-06-24 1986-12-30 Siemens Aktiengesellschaft Photopolymères à base de polyéther
EP0259726A2 (fr) * 1986-09-11 1988-03-16 Siemens Aktiengesellschaft Photopolymères à base d'époxyde
US5049623A (en) * 1989-08-03 1991-09-17 Monsanto Company Ethylenically unsaturated carbamates and coating compositions

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0608891B1 (fr) * 1993-01-28 1999-09-22 National Starch and Chemical Investment Holding Corporation Adhésifs thermofusibles sensibles à la pression durcissables par irradiation
US5998543A (en) * 1996-05-28 1999-12-07 Eastman Chemical Company Stable amino-containing polymer latex blends
US5891950A (en) * 1996-05-28 1999-04-06 Eastman Chemical Company Use of stable amino-functional latexes in water-based inks
US5962556A (en) * 1996-10-22 1999-10-05 Eastman Chemical Company Functional latexes resistant to hydrolysis
US6060556A (en) * 1997-05-21 2000-05-09 Eastman Chemical Company Process for preparing reactive latex blends which are chemically and physically stable until film formation
US6028155A (en) * 1997-05-21 2000-02-22 Eastman Chemical Company Surfactant-containing acetoacetoxy-functional and enamine-functional polymers
US6432614B1 (en) 1998-07-31 2002-08-13 Dai Nippon Printing Co., Ltd. Photosensitive resin composition and color filter
EP0977085A1 (fr) * 1998-07-31 2000-02-02 Dai Nippon Printing Co., Ltd. Composition photosensible à base de résine et filtre couleur
US6558858B2 (en) 1998-07-31 2003-05-06 Dai Nippon Printing Co., Ltd. Photosensitive resin composition and color filter
EP1035439A2 (fr) * 1999-02-25 2000-09-13 Dai Nippon Printing Co., Ltd. Composition photosensible, filtre coloré et résine copolymère destinée à ceux-ci
US6517980B2 (en) 1999-02-25 2003-02-11 Dai Nippon Printing Co., Ltd. Photosensitive resin composition, color filter, and copolymer resin useful for them
EP1035439A3 (fr) * 1999-02-25 2002-02-13 Dai Nippon Printing Co., Ltd. Composition photosensible, filtre coloré et résine copolymère destinée à ceux-ci
US7550556B1 (en) 1999-08-11 2009-06-23 Dai Nippon Printing Co., Ltd. Highly stable resin, hardenable resin composition, production method therefor, color filter and liquid crystal panel
EP1076070A3 (fr) * 1999-08-11 2001-10-17 Dai Nippon Printing Co., Ltd. Résine stable, composition de résine durcissable, procédé pour la préparation, filtre couleur et panneau à cristal liquide
EP1076070A2 (fr) * 1999-08-11 2001-02-14 Dai Nippon Printing Co., Ltd. Résine stable, composition de résine durcissable, procédé pour la préparation, filtre couleur et panneau à cristal liquide
WO2001027182A1 (fr) * 1999-10-08 2001-04-19 Dai Nippon Printing Co., Ltd. Resine durcissable a photosensibilite elevee, composition de resine photodurcissable, procede de production correspondant, filtre couleur et panneau d'affichage a cristaux liquides
EP1429184A1 (fr) * 2002-12-12 2004-06-16 Shipley Company, L.L.C. Copolymère fonctionnalisé pour composition photopolymérisable
WO2005103822A2 (fr) * 2004-04-22 2005-11-03 Showa Denko K.K. Composition de résine photosensible, produit vulcanise a partir de celle-ci et procédé de fabrication de carte à circuit imprimé utilisant ledit produit
WO2005103822A3 (fr) * 2004-04-22 2006-12-14 Showa Denko Kk Composition de résine photosensible, produit vulcanise a partir de celle-ci et procédé de fabrication de carte à circuit imprimé utilisant ledit produit
KR100808070B1 (ko) * 2004-04-22 2008-02-28 쇼와 덴코 가부시키가이샤 감광성 수지 조성물, 그 경화물 및 그것을 사용하는 프린트배선 기판의 제조 방법
US7790354B2 (en) 2004-04-22 2010-09-07 Showa Denko K.K. Photosensitive resin composition, cured product thereof and production method of printed circuit board using the same
US8546485B2 (en) 2010-12-20 2013-10-01 Henkel Corporation Photocurable dicing die bonding tape
CN113801294A (zh) * 2021-08-10 2021-12-17 华南理工大学 一种高强度和宽温域高阻尼聚氨酯弹性体材料及其制备方法
CN113801294B (zh) * 2021-08-10 2022-11-18 华南理工大学 一种高强度和宽温域高阻尼聚氨酯弹性体材料及其制备方法

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