NO752955L - - Google Patents

Description

Polymerizable composition

The present invention relates to compounds with multiple acrylic radicals, compositions containing these and methods for producing them. The invention also relates to the use of these compounds and compositions.

The compounds with multiple acrylic radicals according to the present invention are mixtures whose average composition has the general formula

where X are radicals derived by removing OH groups from COOH groups of an organic carboxylic acid containing u COOH groups and whose number of carbon atoms is between 14 and 90, preferably between 18 and 54,

Y is the radical derived by removing m-p hydrogen atoms from the hydroxyl groups in an organic compound containing m OH groups,

Z is the radical radical derived by removing the OH group from the COOH group of an organic monocarboxy1 acid containing at least one terminating CH2=CH-COO radical,

n is an integer from 1 to 6 and preferably from 1 to 4,

m is an integer from 2 to 8 and preferably from 3 to 6, and

p_ is a number from 0 to 2.5

provided that m-p-1 is a positive number different from 0 and that n(m-p-l) is between 2 and 15.

It is essential that the organic carboxylic acid, whose radical is denoted X in the general formula given above, has the hydrophobic character of a higher fatty acid, and for this reason it contains 14 to 90 carbon atoms and preferably 18 to 54 carbon atoms. The organic carboxylic acid radical can be saturated to unsaturated and straight-chain or branched, and in addition contain from 1 to 6 and preferably 1 to 4 carboxyl groups. Instead of the free acid, it is also possible to use functional derivatives, such as acid halides, anhydrides, esters, salts or the like. According to the invention, however, it is also possible for certain applications to replace up to 75 mole percent of the organic carboxylic acid containing at least 14 carbon atoms with one or more mono- or polycarboxylic acids containing less than 14 carbon atoms, such as adipic acid, maleic anhydride, HET acid, tetrabromophthalic anhydride , isophthalic acid or the like.

Examples of monocarboxylic acid XOH (n = 1) which can be used in the compound according to the invention include the saturated and unsaturated monocarboxylic fatty acids containing at least 14 carbon atoms, such as myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lingoseric acid, certoic acid, monotannic acid, oleic acid, risnusol -j esic;;; linoleic acid and linolenic acid, mixtures of fatty acids derived from vegetable fats, such as palm oils, linseed oil, dehydrated or non-dehydrated castor oil, perilla oil, soybean oil, safflower oil, Chinese wood oil, oiticica oil, cottonseed oil, tall oil and the like, mixtures of fatty acids derived from animal fats, such as tallow, lard, whale oil, fish oils and the like, and saturated and unsaturated synthetic fatty acids with the above stated number of carbon atoms.

Examples of dicarboxylic and polycarboxylic acids are X(OH) « (n-.-.- = 2 to 6) which can be used in the compounds according to the invention are dimerized and trimerized fatty acids derived from fatty acids containing two or three double bonds, such as the commercial Empol -products from Emery Industries, Inc. and the Hystren products from HuncoChemical Products Ltd., the dimer of methyl 1 -1'inol at, chlorides of these dimers, lower dicarboxylic acids with a long chain hydrocarbon radical, e.g. dodecyl, tetradecyl, hexadecyl and octadecyl succinic acids and the like, and also the lower dicarboxylic acids with a thiohydrocarbon radical, e.g. dodecylthiosuccinic acid and the like, Diels-Alder addition products of maleic anhydride with a fatty acid or a drying oil containing conjugated double bonds, e.g. conjugated linoleic acid, α or β-eleostearic acid, Chinese wood oil, oiticica oil and the like, reaction products of maleic anhydride with fatty acids or oils containing one or more unconjugated double bonds, reaction products of polycarboxylic acids or their anhydrides (maleic acid, succinic acid, phthalic acid, trimellitic acid, pyromellitic -acids and anhydrides and the like) with hydroxylated long-chain compounds, e.g. rice oleic acid, higher fatty alcohols, epoxidized higher fatty acids, oils containing hydroxylated higher fatty acids, e.g. castor oil, or epoxylated natural oils, polycarboxy1 acids prepared from an alkyd resin containing higher fatty acid radicals and an excess of di- or polycarboxylic acid, which are respectively alkyl resins rich in carboxyl groups, which alkyd resins are rich in carboxyl groups obtained by condensing a dimer or trimeric acid containing at least 14 carbon atoms and a di-acid with a chain shorter than 14 carbon atoms with a poly-hydroxylated compound, addition products of lower to higher mono- or polycarboxylic mercaptoic acid are with unsaturated fatty acids, oils or alkyd resins, such as the addition product of mercaptosmaric acid with linseed oil, the addition product of thioglycolic acid with linolenic acid and the like, brassylic acid (High Polymers, vol.2_7, Wiley-Intersciences, p88-91), dicarboxylic acid with 19 carbon atoms is obtained by the KOCH synthesis, according to the OXO synthesis The ROELEN and REPPE reaction (High Polymers, vol.2_7, Wiley-Intersciences, p.97-llo), and the like.

The organic compound whose radical is denoted Y in the above general formula contains from 2 to 8 and preferably from 3 to 6 hydroxyl groups in the molecule. It can be a diol such as ethylene glycol, propylene glycol, 1,4-, 1,3-, or 2,3-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, polyethylene glycols, polypropylene glycols or the like. However, preferably the hydroxylated compound contains at least three hydroxy groups, and examples of these include glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, di-pentaerythritol, tripentaerythritol, sorbitol, mannitol, inositol, pinitol, quebrachitol, α-methyl glycoside and the like, as well as hydroxy len product obtained by condensation of ethyl en or propylene oxide with the polyalcohols specified above. It is also possible to use polyhydroxylated polymers such as polyether alcohols and polyester alcohols as well as their oxyalkylation products with ethylene oxide or propylene oxide.

The organic monocarboxylic acids containing at least one terminating CH2=CH-COO radical which provides the monovalent radical Z include e.g. in the case of acrylic acid, the reaction product of one mole of a saturated or unsaturated dicarboxylic acid or anhydride with one mole of a hydroxyalkyl acrylate, e.g. the reaction product of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, 8-hydroxyoacyl acrylate, 10-hydroxydecyl acrylate, 12-.hydroxydodecyl acrylate or the like with succinic anhydride, maleic anhydride, phthalic anhydride, adipic acid, sebacic acid, itaconic acid or the like, the reaction product of two moles of a hydroxyalkyl acrylate with one mole of a tricarboxylic acid or anhydride, such as trimellitic anhydride, aconitic acid or citric acid, the reaction product of three moles of a hydroxyalkyl acrylate with one mole of a tetracarboxylic dianhydride or acid, such as pyromellitic anhydride or acid, or any other organic compound containing at the same time at least one free carboxylic acid group (or the chemical equivalent of a carboxyl group, such as an acid halide, anhydride, ester, salt or similar group) and at least one terminating CH2=CH-C00 radical.

Different methods are possible for the preparation of compounds with multiple acrylic radicals corresponding to the above-mentioned formula.

One-Step Process (Process #1)

S stoichiometric amounts of the constituents which provide the radicals X, Y and Z in the above general formula (ie one mole of the higher organic carboxylic acid X(OH)n, n moles of the organic compound YH^ and n(m-l) moles of monocarboxylic acid a ZOH with at least one terminating CH2=CH-COO radical) is heated in an organic, water-attracting solvent (benzene, toluene or the like) in the presence of a radical polymerization inhibitor (hydroquinone, copper oxide or the like), an esterification catalyst (sulfuric acid, p-toluenesulfonic acid or the like) and optionally an additive to prevent the color of the products obtained (e.g. triphenyl phosphite or the like). The reaction can be carried out at atmospheric pressure, preferably in an inert atmosphere (nitrogen or the like) at a temperature of 70 - 140°C

in the course of 2 to 10 hours during the removal of forest in gsv an et wood

using solvent et.

The reaction is stopped as soon as the desired degree of esterification (measured in accordance with the amount of esterification water collected) is reached.

After having removed in a known manner the solvent, the catalyst, excess inhibitor and any excess of monocarboxy 1-acid ZOH containing at least one terminating CH2=CH-COO radical, a product according to the invention is obtained which can be used either untreated or after suitable cleaning for different applications.

The reaction product thus obtained is a mixture of compounds with a given molecular weight distribution, which can be shown by gel permeation chromatography whose average composition, however, has the general formula I stated above. The products according to the invention have a well-defined content of hydroxyl groups. In formula I, p represents an average number of free hydroxyl groups that remain unreacted in the final product after esterification.

This one-step process is preferred for economic reasons and because of its ease of feasibility. However, similar end products with an intermediate composition of formula I can be obtained by one of the following two-step processes.

Two-stage processes (Processes no. 2a and 2b).

(a) Under esterification conditions similar to those described for the one-step process, first the organic compound YH^ is esterified with the higher organic carboxylic acid X(OH)n, after which residual hydroxyl groups in the organic compound YHm are esterified with monocarboxylic acid a ZOH containing at least one terminating CH2=CH-COO radical.

(v b) 'Alternatively, the organic compound YH is first esterified with monocarboxylic acid ZOH, with only one hydroxyl group preferably being allowed to remain in the organic compound Y. H m', after which this is esterified with the higher organic carboxylic acid X(OH)n.

In the one-step process or the two-step processes, the free acids X(OH)n and ZOH can be replaced by halides, preferably chlorides or anhydrides of these acids. Especially when it comes to acid halides, these make it possible to carry out the esterification reaction at more moderate temperatures, e.g. below 4o°C, and in this case it is advantageous to carry out the esterification in the presence of an acid acceptor, such as pyridine, triethylamine or the like.

In addition, the compounds according to the invention can also be obtained by transesterification of the organic compound YH with lower lower alkyl esters of the acids X(OH) and ZOH. In this case, the transesterification is carried out in a solvent carrier having a sufficiently high boiling point (e.g. toluene or the like) to ensure that the reaction takes place at the boiling temperature of the mixture at a sufficient rate and that an azeotropic mixture is formed with the lower alcohol released by transesterification. The rate of transesterification is monitored by measuring the amount of lower alcohol thus released and collected.

In Table I below, some non-limiting examples are given of compounds with multiple acrylic radicals according to the present invention. The table shows the number of the compound with multiple acry 1 radicals, the nature and the molar amount of each of the components X, Y and Z, together with the number indicating the manufacturing process, (1 = one-step process, 2a = two-step process with reaction first between X(OH) and YHm, 2b = two-step process with reaction first between YH and ZOH). *

The abbreviations used in the table have the following meanings:

ADA : adipic acid

MA : maleic anhydride

PA : phthalic anhydride

HEA : hydroxyethyl acrylate

HPA : 2-hydroxypropyl acrylate

(ADA + HEA) : addition product of adipic acid and hydroxyethyl acrylate (MA + HEA) : addition product of maleic anhydride and hydroxyethyl acrylate (PA + HEA) : addition product of phthalic anhydride and hydroxyethyl acrylate (MA + HPA) : addition product of maleic anhydride and 2-hydroxypropyl acrylate dimer acid = EMPOL (Emery Industries Inc.): dicarboxylic acid dimerization products of C 2 g unsaturated monobasic fatty acids. The dimerization reaction may over time leave a certain percentage of unpolymerized monobasic acid and/or form a certain percentage of trimeric acid. According to the composition of the dimer obtained, several commercial products are characterized by a number following the registered trademark EMPOL. Thus EMPOL 1010 is the purest commercial dibasic dimer, containing only 3% trimer and no monobasic acid,

EMPOL 2022 is a dimer acid containing 19-22% trimer

and 5% monobasic acid,

EMPOL lo38 is the same as the previous one but less farnot.

Dimer acid chloride; acid chloride of EMPOL.

PLURACOL SP 760: the addition product of approx. 12 moles of ethylene oxide on a

mol sorbitol, with a molecular weight of approx. 700 PLURACOL PeP 450: the addition product of approx. 7 moles of ethylene oxide on a

moles of pentaerythritol with a molecular weight of approx. 400 TERCAROL G 310 (glycerol + 3 moles of propylene oxide, molecular weight of approx. 310) tetracid: esterification product of one mole of pyromellitic acid with four moles of rice oleic acid.

triacid: addition product of two moles of thioglycolic acid to one mole of linolenic acid.

Two remarks are necessary in connection with the above-mentioned table: 1) The respective molar amounts of the components X, Y and Z used for the preparation of the compounds with multiple acrylic radicals according to the present invention were determined taking into account the number of carboxyl groups and hydroxyl groups present in the three components. Nevertheless, important deviations can be made with regard to these amounts, as products are still obtained within the framework of the invention. 2) The end product obtained from the same starting materials by the different methods has a different molecular weight distribution which can be shown by gel permeation chromatography. The products obtained by the two-step process have a wider molecular weight distribution than products obtained by the one-step process.

The compounds with multiple acry1 radicals according to the present invention are liquid to waxy substances, whose viscosity at ambient temperature is between a few poise and several hundred poise. They are colorless to dark brown compounds, depending on the quality of the raw materials and the operating conditions used during the synthesis process. They have good solubility in aromatic solvents, ketones, esters and the like, as well as in mono- and polyfunctional vinyl and acrylic monomers. Their vapor pressure at ambient temperature is practically negligible. The hydrophobic character is more or less clear, depending on the raw materials used in their production.

The present invention also relates to the reaction product obtained by reacting a mixture of compounds with the average composition according to formula I where p is greater than zero, with aliphatic, cycloaliphatic, heterocyclic or aromatic mono- or di-isocyanates. The properties of the urethane-modified products differ from the unmodified starting products by a higher viscosity and a lower hydroxyl number. Photopolymerizable inks and printing inks formulated with these modified resins wear faster than the corresponding unmodified products. Due to an improvement in the rheological properties and a better equilibrium between the hydrophobic/hydrophilic balance in the molecule, ultraviolet-drying offset ink formulations including certain urethane-modified products have better printing properties on htiy speed printing presses. Mechanical properties and chemical resistance of the cured film are improved by using the urethane-modified products.

Non-limiting examples of isocyanates include the following monoisocyanates: methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, cyclohexyl isocyanate and phenyl isocyanate, the following diisocyanates: hexamethylene diisocyanate, trimethylhexyl diisocyanate, dimer fatty acid diisocyanates such as DDI manufactured by General Mills Chemicals, isoferon diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate and diphenylmethane-4,4•-diisocyanate,

and urethanized adducts obtained by reacting diisocyanates with monoalcohols.

In a preferred embodiment for the production of these urethane-modified compounds, from 2 to 20% by weight of mono- or diisocyanates are gradually added to the compounds with the then average composition of formula I in the presence of known catalysts, such as dibutyltin dilaurate, triethylendiamine, etc. .The reaction is introduced between

OE OE '

40 and 80 C, preferably between 55 and 70 C, possibly in the presence of inert solvents. To allow a certain number of unreacted hydroxyl groups to remain in the final product, the molar ratios between isocyanate and hydroxyl groups in the reacting products are chosen below equilibrium.

To lower the viscosity, there is e.g. possible to reduce the molecular weight of the compounds according to the invention by partial transesterification in a known manner, with a mono- or polyalcohol, such as methanol, ethanol, ethylene glycol, hydroxyalkyl acrylate or the like with a molecular weight below 2CO.

Due to the presence of a majority of acryl unsaturated groups

in the molecules, the compounds according to the invention are polymerized easily and can form trees while ionic or cross-linked polymers under the following conditions, under the influence of heat at a temperature between 50

and 250°C, preferably between 50 and 150°C, preferably in the absence of oxygen, by the addition of radical initiators which split at a higher temperature (e.g. above 40°C) or even at ambient temperature provided that an accelerator is added, by exposing the product to ionizing radiation of an electromagnetic nature (gamma rays or X-rays) or the article beam (accelerated electrons),

even in the presence of air and without the need for any addition, in the visible and/or ultraviolet light, provided that a photosensitive agent or photoinitiator is added.

The compounds with multiple acrylic radicals according to the present compound can therefore be advantageously used as film-forming binders for all applications where rapid polymerization is necessary, and can be used either alone or mixed with other materials, such as inert non-copolymerizable polymers, reactive copolymerizable polymers, copolymerizable oligomers, inert plasticizers, inert organic surfactants, copolymerizable olefinically unsaturated monomeric compounds and various auxiliaries.

As examples of inert polymers, the following can be mentioned in particular; polyolefins, polystyrene, polyalkylacrylates, polyvinyl chloride, polyvinyl acetate, polyethers, polyamides, saturated polyesters, alkyl resins, epoxy resins, urea formaldehyde resins, aryl sulfonamide formaldehyde resins, terpene phenol resins, polyvinyl alkyl ethers, chlorinated rubber, cellulose esters, (acetopropionate, aceto -butyrate or the like), copolymers of vinyl chloride with vinyl acetate, maleic esters, vinylidene chloride, vinyl esters or the like.

Examples of reactive copolymerizable polymers include the unsaturated polyesters and unsaturated alkyd resins, unsaturated resins obtained by reacting an unsaturated hydroxylated compound (e.g. allyl alcohol, hydroxyethyl acrylate or the like) with the addition product of a polyisocyanate (e.g. toluene diisocyanate, hexa- methylene diisocyanate or the like) and a resin with free hydroxyl groups (e.g. a hydroxylated polyether, a hydroxyalkyl acrylate copolymer, a hydroxylated polyether or the like), this addition product still containing free NCO groups. As examples of other reactive resins that can be used according to the invention, reference is made in particular to A. Vrancken, XI th Fatipec Congress, June 11-16, 1972, Florence, pages 19 to 41.

The copolymerizable oligomers which can be added to the polymerizable compounds according to the invention are used in principle when it is necessary to modify the viscosity, the flow limit or the binding end, with the aim of adapting the resulting products to different applications and/or technical applications. They are used in particular to reduce the viscosity of the product obtained. At the moment of polymerization, these polymers copolymerize with the compounds according to the invention and form part of the thus obtained compositions. Examples of copolymerizable oligomers include di-, tri- and polyacrylates of hydroxylated products obtained by condensation of ethyl enoxyde or propyl enoxyde with glycerol, trimethylolpropane, pentaerythritol, sorbitol or the like.

The inert plasticizers which can be added to the compounds with multiple acrylic radicals according to the invention can be esters of organic acids or inorganic acids, such as o-, iso- or terephthalic acid, adipic acid, azelaic acid, sebacic acid, citric acid or phosphoric acid, with mono- or polyhydroxy aliphatic and aromatic hydroxylated compounds, such as butanol, 2-ethylhexanol, phenol, cresol, diethylene glycol, triethylene glycol, dipropylene glycol or the like. It is also possible to use epoxidized oils, chlorinated paraffins, chlorinated polyphenyl compounds, chlorinated naphthalenes or the like as plasticizers.

If desired, it is possible to add inert organic solvents, such as ethyl acetate, methyl ethyl ketone or the like to compounds with multiple acrylic radicals according to the invention, these solvents being mainly added to reduce the viscosity. Nevertheless, it is preferred not to use solvents because of problems with regard to recycling, toxicity and pollution caused by the solvents, which are thus eliminated. As indicated above, according to the invention it is actually possible, based on the compounds with multiple acry1 radicals, to regulate the viscosity of the compositions so that the viscosity can vary from a few poise to several thousand poise at 25°C,

and thus make the use of organic solvents inevitable.

On the other hand, it can be advantageous to use copolymerizable olefinically unsaturated monomers together with the compounds according to the invention. Depending on a computational application, these monomers may be volatile or non-volatile and may contain one or more olefinically unsaturated bonds. Examples of these copolymerizable olefinically unsaturated compounds include styrene, vinyl acetate, vinyl chloride, vinylidene chloride, mono-, di-, and polyacrylates of di-, tri-, and polyols, such as trimethylolpropane triacrylate, pentaerythritol tri- and tetraacrylate, and the like. Like the copolymerizable oligomers previously indicated, the copolymerizable olefinically unsaturated monomers can be added to the compounds with multiple acrylic radicals according to the invention to modify the viscosity and in copolymerized form it will form part of the final polymer products thus obtained.

The following additives can be added to the compound according to the present invention: known heat and light stabilizers, known antioxidizing agents, known viscosity modifying agents or thixotroping agents, known flow agents, chain transfer agents that serve to accelerate the radical polymerization as soon as it has started (examples of these agents include di- and triamines, alkanolamines, monoalkyl dialkanolamines and dialkylmonoalkanolamines, morpholine and its derivatives, polyamines, N-phenylglycine and its derivatives, N,N<«->dimethylmonoethanolamine monoacrylate, N-methyldiethanolamine diacrylate, triethanolamine triacrylate and the like). Polymerization inhibitor intended to effect stability during storage (e.g. quinones, hydroquinones, substituted phenol derivatives, primary aromatic amines, copper compounds and the like), waxes, for the purpose of obtaining scratch-free cured films, which waxes may be natural, such as candelilla wax, Carnauba wax or the like, or synthetic such as polyethylene, polypropylene or paraffin wax, chlorinated paraffins, chlorinated naphthalenes or the like, pigments that have dyes, mineral or organic fillers, fibrous or powdery reinforcing agents and the like.

The compounds according to the invention can be used for various purposes, and certain non-limiting examples of such are given in the following.

By adding radical initiators (peroxides, hydroperoxides, percarbonates, azo compounds or the like) which split under the influence of heat, the compounds according to the invention can be used as stbpe resin, press-stop resin, sprby-stop resin and e'oft r udering resin. Due to the excellent flexibility of the products obtained according to the invention, it can be added to polyvinyl chloride plastisols in an amount of 5 - 30% by weight of the total composition, as reactive plasticizers to aid in addition to the metal sheets and to increase the cohesive power of the applied film.

When adding accelerators to some of the initiators described above, e.g. e.g. by adding dimethyl 1-p-toluidine to benzoyl peroxide, cobalt naphthenate to methyl ethyl ketone peroxide or the like, the polymerization of the compositions according to the invention can be initiated at ambient temperature. Compositions of these formulations can in particular be used as road marking paints. In this particular case, paraffin is added to the formulations so that the paraffin separates out after application to the substrate and forms a surface film which provides protection against the effects of atmospheric oxygen. Another typical application of the composition according to the present invention is anaerobic adhesives in which initiator-accelerator pairs are appropriately chosen. These compositions have the property that they do not polymerize in the presence of air, so that they can be stored for several months at ambient temperature. However, if the presence of oxygen is omitted, these adhesives will begin to polymerize slowly. Furthermore, the presence of metallic ions such as iron ions has the effect of significantly increasing the rate of polymerization so that they can be used to lock metallic compounds under anaerobic conditions,

In the complete absence of initiators, accelerators and the like, the compositions according to the invention can be polymerized very quickly by accelerated electron beam curing. They can therefore be used for the production of varnishes, paints, coatings or the like and serve as industrial coatings on a large number of substrates, in particular wooden boards, cardboard, fiber boards, hard wood fiber boards, paper, metal, asbestos cement and the like.

If photosensitive agents and/or photoinitiators are added to the compositions according to the invention, compositions are obtained which can polymerize under the influence of light with one or more wavelengths between 200 nm and 5000 nm. The photosensitive agents are supplied to all molecules containing one or more unsaturations or to the initiator part of the energy transferred by the light. By means of the unsaturated system or systems or of the photoinitiator, the photosensitive agents form free radicals or ions that initiate polymerization or the cross-linking of the composition.

With regard to the photosensitive agents or photoinitiators that can be used according to the invention, reference is made in particular to G. Delzenne, Ind.Chim.Belge, 24, 739-764/1958<»>J.Kosar, "Light Sensitive Systems", pub. Wiley, New York, 1965; N. J. Turro, "Molecular Photochemistry", pub. Benjamin Inc., New York, 1967, H.G. Heine et al., Angew. Chem. 84, 1032/1972.

Photoinitiators are mainly chemical compounds belonging to one of the following main categories: Compounds containing carbonyl groups such as pentanedione, benzyl, piperonal, benzoin and its halogenated derivatives, benzoin ethers, anthraquinone and its derivatives, p,p'-dimethylaminobenzophenone, benzophenone and the like, compounds containing sulfur or selenium, such as di- and polysulfides, xanthogenates, mercaptans, dithiocarbamates, thioketones, beta-naphthoselenazolines, peroxides, nitrogen-containing compounds such as azonitriles, diazo compounds, diazides, arcidine derivatives, phenazine, quinoxaline, quinazoline and oximesters, e.g. . 1-phenyl,1,2-propanedione 2-[0-(benzoyl)oxime], halogenated compounds such as halogenated ketones or aldehydes, methylaryl halides, sulfonyl halides or dihalides, and photoinitiator dyes, such as diazonium salts, azoxybenzenes and derivatives , rhodamines, eosins, fluorsins, acriflavin or the like.

The photosensitive agents belong to one of the following categories: ketones and their derivatives, carbocyanines and methines, polycyclic aromatic hydrocarbons, such as anthracene or the like, and dyes, such as xanthenes, safranins and acridines.

After the addition of 0.1 to 10% by weight of photoinitiators and/or photoflammable agents, the products according to the invention or mixtures containing these products can be used for the production of translucent varnishes for coating a large number of substrates, e.g. those previously indicated in connection with the polymerisation ion with accelerated electron trawl are.

They can also be used for the production of semi-translucent sealants that have a high content of translucent fillers and colored sealants containing dyes that are translucent for part of the lamp's emission spectrum. The fillers are chosen so that they have minimum absorption at wavelengths from 200 to 700 nanometers in the spectrum. They include, in particular, precipitated or micronized calcium or magnesium carbonate (calcite, aragonite or the like), barium or calcium sulfate (baryte, barite white or the like), micronized hydrated potassium or magnesium silicoaluminate, micronized magnesium silicate, precipitated hydrated aluminum oxide, asbestosin, micronized or non-micronized talc and the like.

The photopolymerizable compounds according to the invention can also be used as laminating agents or glues to bond safety glasses, laminated wrapping films or compositions, provided that at least one element of the bonded material is translucent to ultraviolet radiation.

They can also be used in printed circuits, relief and gravure printing plates, photo reproduction, photoresistors and the like.

A particularly advantageous area of application for the compounds according to the invention is in solvent-free, ultraviolet ink, i.e. ink which smokes and hardens under the influence of ultraviolet rays. In this particular case, very thin pigmented or colored coatings of these inks are applied which, due to the low applied thickness, allow the penetration of ultraviolet radiation to a sufficient depth to initiate photopolymerization with a very high initiation rate.

Solvent-free ink is of interest in connection with the fight against air pollution. Conventional printing inks contain up to 45% hydrocarbons which are removed in ovens. Solvents are released into the atmosphere together with the combustion gases. This can be prevented by expensive installations for catalytic or thermal afterburning. In the event of the press being stopped due to an accident, however, the paper in the oven could ignite and thus give rise to a fire and considerable costs with respect to reconstruction.

The use of ultraviolet ink reduces overcrowding in a printing press equipped with sheet-fed presses. Used ultraviolet ink has greater mechanical strength and chemical resistance, while the wear rate is significantly reduced, resulting in less waiting time for completion, with a reduction in stacks of printed material during the production process and elimination of the use of anti- contamination powders, which is the cause of wear of certain parts of the press and entails difficulties in the subsequent final processing, e.g. film lamination.

The use of inks, varnishes or laminate-binding products by ultraviolet irradiation is a known technique that is described in numerous patents. Nevertheless, the quality of products available on the market has delayed their entry into the graphics industry. In particular, some known ultraviolet inks have insufficient storage stability or unsatisfactory drying properties, while others have good drying properties but to an even greater extent entail significant difficulties with respect to achieving water/ink balance in the offset process, which difficulties can result in foaming or unmistakable colouring. Furthermore, the reproducibility with different production rates must be considered insufficient due to the lack of definitions of chemical and physical characteristics (or control standards) that must be observed by the unsaturated pre-polymers and unsaturated monomers and/or oligomers, which are used in the composition of these inks.

The products according to the invention are very suitable for the production of offset inks, letterpress inks and flexiographic inks and also inks used in copperplate printing, engraving and silk-screen printing, which use under ultraviolet irradiation.

The composition of inks and varnishes which are photopolymerizable by ultraviolet irradiation (abbreviated as UV ink) according to the invention is as follows:

The polymerizable binder for ultraviolet inks and varnishes according to the invention comprises 5 - 100% by weight of at least one compound with multiple acrylic radicals according to the invention and 0 - 95% by weight of at least one compound selected from the group consisting of (a) copolymerizable reactive unsaturated polymers, (b) copolymerizable unsaturated oligomers and (c) copolymerizable unsaturated monomers, where examples of the components (a), (b) and (c) have previously been indicated.

In order to obtain fast-wearing UV ink, the compounds with multiple acrylic radicals according to the invention should on average contain 2-15, preferably 4-9 CH2-CH-COO groups per molecule.

Among these compounds (a), (b) and (c), compounds are selected which have good compatibility with the compounds with multiple acrylic radicals according to the invention and a comparable polymerization reactivity. These compounds are usually used to modify the rheology of the ink or to improve adhesion, e.g. when it comes to printing on tin plate, on aluminium, on plates of plastic material or the like. The compounds (b) and (c) are mainly used to reduce the viscosity of the inks. The monomers (c) are preferably selected from compounds with a negligible volatility at 25°C and a high acrylic radical content, e.g. trimethylolethane triacrylate, trimethylolpropane triacrylate, glycerol triacrylate, butane-1,2,4-trioltriacrylate, pentaerythritol, tri- or tetraacrylate, dipentaerythritol tetra-, penta- or hexaacrylate or the like.

The inert polymers and plasticizers in the ultraviolet inks according to the invention are selected from the previously indicated products, taking precautions to ensure good compatibility with the photopolymerizable binder and the other components of the ink, absence of chemical reaction with other components of the ink and low absorption in the ultraviolet spectrum. The inert polymers are added to adapt or modify the printability properties, the final appearance (gloss) and the properties of the resulting ink films. The plasticizers are used in particular to loosen the photoinitiator and/or the photosensitive agent or other auxiliary substances.

The pigments and fillers for the ultraviolet inks according to the invention are added to impart colorimetric properties. An ink or varnish may contain 0 - 30%, preferably between 0 and 18% organic pigments which are translucent and semi-translucent to ultraviolet rays, 0 - 60% mineral coating pigments, and 0 - 50% fillers which are translucent to ultraviolet rays rays, the total amount of fillers and pigments being between 10 and 60% in the case of ultraviolet inks and 0% in the case of overprinting. These pigments and fillers must neither delay nor inhibit the photopolymerisation of the photopolymerizable binder. They must also not react chemically with the photoinitiator or photoinitiators and/or the photosensitive agents, or adsorb these physically.

The organic pigments can be selected from the products listed in the Color Index, whose absorption at wavelengths of 200 to 500 nanometers is as low as possible.

The use of opaque or covering mineral pigments is necessary for the production of white inks, which is the case e.g. with offset ink intended for printing on tin plate. Examples of opaque pigments include titanium, zinc, iron or chromium oxides, zinc or cadmium sulphides, manganese or ammonium phosphates, cobalt aluminates or the like. It goes without saying that the absorption of the ultraviolet rays by these opaque pigments is higher than with organic pigments that are translucent to ultraviolet rays and that ink formulated with these opaque pigments requires higher irradiation energy (expressed in milliwatts per cm of printed surface). In other words, the number of ultraviolet irradiators must be increased to achieve the same rate of consumption.

The fillers which are translucent to ultraviolet rays and intended for use in inks according to the invention, which were previously indicated in connection with transfer materials, can be added to modify the ink's rheological properties.

The photoinitiators and the photosensitive agents and also the various additives suitable for ultraviolet inks have already been indicated.

The compounds according to the invention are characterized by a balance between lipophilic and hydrophilic parts of the molecule, which makes them particularly suitable for use in formulations for ultraviolet offset inks. In contrast to the binders currently used in the ultraviolet offset inks, the balance between ink and evaporating solvent can easily be achieved and maintained in the press, even after a stop in printing, when compounds according to the invention are used. The isopropanol content in the order of 15 - 20% can be used without difficulty in continuously steaming systems. Among the compounds according to the invention, the best offset-eg ens caps are obtained with those with a hydrofill number between 10 and 80, and preferably between 20 and 65, and with an acid number between 2 and 25, preferably between 5 and 15. The products according to the invention entails a particular advantage that they exhibit complete inertia towards the ink conveying rollers and towards the dot cloths which transfer the ink from the plate cylinders to the substrate. The compounds according to the invention must have a viscosity between 2 and 250 poise, and preferably between 30 and 200 poise in the case of inks intended for rotary offset and letterpress presses, and a viscosity of between 50 and 400 poise, preferably between 130 and 200 poise for inks to sheet-fed offset presses or letterpress presses. The compounds according to the invention whose viscosity is less than 30 poise, possibly mixed with photopolymerizable monomers and/or oligomers, can be used for the formulation of flexiographic inks, screen printing inks and gravure inks.

The following examples illustrate the invention. All parts are by weight unless otherwise stated.

Example 1

A fraction of the hydroxyl groups of a polyol containing

6 hydroxyl groups per molecule (Pluracol SP760) was first esterified with a fatty monoacid in a double-walled glass reactor of 3 liters and equipped with a rebarer, a thermometer and an azeotropic distillation column. For this purpose, the following amounts of reactants were introduced into the reactor: 680 g of sorbitol - 12 mol of ethylene oxide addition product

(Pluracol SP760),

423 g oleic acid,

300 g of benzene,

40 g of p-toluenesulfonic acid,

1 g of cupric oxide.

The mixture was boiled at atmospheric pressure. When 27 ml of esterification water had been collected by azeotropic distillation of the mixture, it was cooled to a temperature below 50°C and the following was added:

480 g acrylic acid

130 g of benzene

1 g of copper (I) oxide

The mixture was again brought to boiling and the esterification

was continued until no more water passed over by azeotropic distillation.

The mixture was cooled and 5 liters of benzene was added, after which it was washed respectively with aqueous solutions of sodium chloride and sodium bicarbonate until neutral. 500 ppm hydroquinone was added and the unsaturated ester was isolated by distilling off the solvent in vacuo.

The final product had the following characteristics:

Viscosity: 2.5 poise at 25°C

OH value: 29

Acid value: 11

Acrylic unsaturation: 3.1 mech/g (mech. = milliequivalent of

acrylic acid)

Colour: yellow

The viscosity was measured with a Hbppler viscometer. The acrylic unsaturation was calculated from the intensity of the band at 804 cm<-1> in the infrared absorption spectrum, measured in a solution of the product in carbon disulphide.

Example 2

The procedure according to Example 1 was repeated but oleic acid was replaced with 220 g of an addition product of maleic anhydride and oleic acid. This product was obtained by reacting a mixture of 1.2 mol of maleic anhydride with 1 mol of oleic acid at 200°C for 6 hours in a shard of glass at atmospheric pressure. Any excess of maleic anhydride sublimed during the reaction, the remaining was evaporated after the end of the reaction. This addition product had an acid number of 385 and an average maleic anhydride acid content of 0.7 mol per moles of oleic acid.

The final product obtained under the experimental conditions specified in Example 1 had the following characteristics:

Viscosity: 55 poise at 25°C

OH value: 27

Acid value: 15

Acry 1 unsaturation: 4.3 mech./g

Example 3

The procedure in Example 1 was repeated, but instead of oleic acid, 750 g of an addition product of maleic anhydride and linseed oil were used. This addition product was prepared by reacting 1800 g of linseed oil (iodine number = 190) and 200 g of maleic anhydride at 250°C for 4 hours in an autoclave. The iodine number was then 135, the acid number was 110 and the color of the product obtained was yellow. The addition product contained an average of 1 mol of maleic anhydride per moles of linseed oil.

The final product obtained under the experimental conditions specified in Example 1 had the following characteristics:

Viscosity: 72 poise at 25 C

OH value: 19

Acid value: 7

Acrylic unsaturation: 2.2 mech./g

Example 4

The oleic acid according to Example 1 was replaced with 190 g of

an addition product of maleic anhydride and (3-eleostearic acid. This last product is obtained by a Diels-Aid reaction according to the procedure described by R.S. Morrell and H. Samuels (J.Chem.Soc. 1932, 2251 - 54). The reaction is exothermic and takes place rapidly at 85 - 90°C. The product contains one molecule of maleic anhydride per molecule of B-eleostearic acid and is present in the form of a yellow-white solid with a melting point of 77°C. The final product obtained under the experimental conditions specified in Example 1 had the following characteristics:

Viscosity: 85 poise at 25°C

OH value: 25

Acid value: 14

Acrylic unsaturation: 4.7 mech./g

Example 5

565 g dimer acid containing 19 - 22% trimer and 5% monobasic unpolymerized acid (EMPOL 1022 from Eraery Industries Inc.,)

272 g pentaerythritol

576 g of acrylic acid

400 g of benzene

20 g sulfuric acid (d = 1.84)

1 g cupric <-(I)-oxidn

was placed in a double-walled glass reactor of 3 liters equipped with a retort, a thermometer and an azeotropic distillation column.

The mixture was brought to boiling at atmospheric pressure. The esterification water from the azeotropic distillation was collected and the benzene was returned to the reactor. Esterification was complete within 7 hours and 144 ml of water had thus been collected in the first half of this period, as the boiling temperature of the contents of the bottle rose from 92

to 105°C.

This mixture was diluted with 5 liters of benzene and washed respectively with aqueous solutions of sodium chloride and sodium bicarbonate until neutral. 500 ppm hydroquinone was then added and the unsaturated ester was isolated by distilling off the solvent in vacuo. The weight of the product obtained was 1280 g, i.e. approx. 70% of theoretical.

This ester, which was dark brown in colour, had the following characteristics:

Viscosity: 600 poise at 25°C

OH value: 25

Acid value: 6

'Acrylic unsaturation: 5.5 mech./g

less than 0.1% by weight residual benzene.

Example 6

By following the procedure according to Example 5, an unsaturated ester was produced from the following ingredients: 565 g dimer acid, the same as in Example 5, but less

dyed (EMPOL 1038 of Emery Industries Inc.)

408 g pentaerythritol

720 g acrylic acid

500 g of benzene

34 g of p-toluenesulfonic acid

2 g cupric-(I)-oxide

1740 g (approx. 80% of theoretical) of an unsaturated resin which was present in the form of a viscous liquid (230 poise

o

at 25 C), whose color was brown-yellow and which had the following characteristics:

OH value: 30

Acid value: 2

Acrylic unsaturation: 6.5 mech./g

less than 0.1% of residual benzene.

Example 7

By the method according to Example 5, an unsaturated ester was prepared from the following ingredients: 565 g C36dimeric acid containing only 3% trimer (EMPOL

1010 of Emery Industries Inc.)

1360 g of the 1 mol sorbitol-12 mol ethylene oxide addition product (PLURACOL SP60)

864 g of acrylic acid

500 g of benzene

40 g of p-toluenesulfonic acid

2 g of copper (I) oxide

The presentation took place over the course of 10 hours. The resulting unsaturated resin (1750 g) had the following characteristics;

Colour: yellow

Viscosity: 50 poise at 25°C

OH value: 494

Acid value: 4

Acrylic unsaturation: 4.0 mech./g

Example 8

In the reactor described in Example 5, pentaerythritol triacrylate was first produced from the following ingredients:

544 g pentaerythritol

1152 g acrylic acid

440 g of benzene

40 g of p-toluenesulfonic acid

2 g of copper (I) oxide

After 4 hours, the esterification reaction was stopped and excess acrylic acid and benzene were removed from the reaction mixture by passing it twice through a thin-layer evaporator.

The free hydroxyl groups that were still present in the reaction product were then reacted with a dimer acid, and this reaction took place in the same reactor that was used for the partial esterification. The following ingredients were used: 660 g of the impure hydroxylated intermediate 300 g dimer acid (EMPOL 1010, see Example 7)

600 g of benzene

1 g of copper (I) oxide

Esterification was continued for 5 to 6 hours under reflux, after which an unsaturated resin product was obtained which was purified and isolated as described in Example 5.

The unsaturated resin (850 g) had the following characteristics:

Colour: yellow

Viscosity: 90 oiuse at 25 C

OH value: 17

Acid value 9

Acrylic unsaturation: 7.5 mech./g

Example 9

a) 1600 g of castor oil (containing 3.0 mec, OH/g) and 400 g of maleic anhydride were introduced into a reactor as described in Example 5.

The mixture was stirred, heated to 125°C and held at that temperature for 2 hours to form an addition product: castor oil maleic anhydride (abbreviated as COMA) with a viscosity of poise at 25°C.

b) 417 g COMA (see above)

375 g of an addition product of 1 mol pentaerythritol + 7 mol

ethylene oxide with a molecular weight of 400, which addition product is marketed by UGINE-KUHLMAN under the trade name PLURACOL PeP 450 300 g benzene

30 g of a 67% aqueous solution of p-toluenesulfonic acid and

0.4 g of triphenyl phosphite

was passed through the same reactor as was used under point a). The mixture was heated to boiling under nitrogen for 3 1/2 hours and 22 ml of esterification water was collected, after which the solution was cooled under nitrogen.

c) As soon as the temperature of the solution obtained fell below 50°C, 192 g of acrylic acid and 1 g of copper (I) oxide were added and the mixture was

again boiled for 10 hours. The temperature of the mixture reached 105°C at the end of the esterification reaction and 40 ml of water was collected by distillation. The mixture was purified as described in Example 5 and 850 g of product was obtained with the following characteristics:

Viscosity at 25°C: 200 poise

OH value : 42

Acid value 6.7

Acrylic unsaturation: 2.6 mech./g

Content of volatile components: ^0.1%

Example 10

a) In the reactor described in Example 5, the following components were introduced: 283 g dimer acid (EMPOL 1038 of Emery Industries Inc., see Example 6)

73 g of adipic acid

408 g pentaerythritol

792 g of acrylic acid

600 g of toluene

50 g of a 67% aqueous solution of p-toluenesulfonic acid

2 g of copper (I) oxide

The mixture was boiled for 5 hours and the temperature finally reached 116°C, and 235 ml of distilled water was collected. The product was purified as described in Example 5 and 1180 g of a product with the following characteristics and which was ready for use was obtained:

Viscosity at 25°C: 125 poise

OH value: 12

•Acid value: 15

Acrylic unsaturation: 7.6 mech./g

Content of volatile components: <0.1%

b) If 73 g of adipic acid in the formulation according to a) was replaced with 194 g of 1,4,5,6,7,7-hexachlorobicyclo[2,2,1]nept-5-ene-2,3-dicarboxylic acid (HET acid ), a product with the following characteristics was obtained:

Viscosity at 25°C: 440 poise

OH value: 34

Acid value: 12

c) ''.If 73 g of adipic acid according to point a) was replaced with 232 g of bromophthalic acid, a product with the following characteristics was obtained:

Viscosity at 25°C: 275 poise

OH value: 27

Acid value: 8

d) If 73 g of adipic acid according to a) was replaced with 83 g of isophthalic acid, a product with the following characteristics was obtained:

Viscosity at 25°C: 245 poise

OH value: 40

Acid value: 26

Example 11

a) The following components were introduced into the reactor described in Example 5:

102 g of adipic acid

371 g pentaerythritol

592 g of oleic acid

529 g of acrylic acid

420 g of benzene

42 g of a 67% aqueous solution of p-toluenesulfonic acid

1.4 g of copper (I) oxide

1.4 g of triphenyl phosphite

The mixture was boiled under a nitrogen atmosphere. The esterification took place over the course of 7 hours and the temperature reached 101°C and 210 ml of water was collected. The product was purified as described in Example 5 i

Viscosity at 25°C: 12 pois

b) To 40© g of the product prepared in a), the following ingredients were added:

18 g of a mixture of 2,4- and 2,6-toluenediisocyanate

0.4 g of triethylenediamine

The mixture was heated for one hour at 65°C, after which 7 g of n-propanol was added and heating was continued for a further 15 minutes. The urethane product thus obtained now had a viscosity at 25°C of 140 poise.

Example 12

The esterification was carried out in an enamelled metal reactor of 150 liters equipped with an anchor burner and an azeotropic distillation column. The reactor was double-walled with oil heating. The following quantities of reactants were introduced into the reactor:

21.47 kg dimer acid (EMPOL 1010, see Example 7)

20.67 kg pentaerythritol

41.04 kg acrylic acid

20.20 kg of benzene

1.52 kg of p-toluenesulfonic acid dissolved in 1 kg of water 0.076 kg of cupric oxide

0.019 kg of triphenyl phosphate

The mixture was degassed in vacuum to an absolute pressure of 150 mm tg, after which the pressure was brought back to atmospheric pressure under a nitrogen atmosphere. This operation was repeated three times.

The mixture was brought to boiling temperature under reflux and the water was removed. The esterification took place for 7 to 8 hours and at that time 11.44 kg of water had been azeotropically distilled from.

The mixture was cooled and transferred to a 600 liter stainless steel vessel fitted with a screw converter. The mixture was diluted with 300 kg of benzene and washed twice with aqueous solutions of sodium chloride and then with aqueous solutions of sodium bicarbonate.

The organic solution purified in this way was stabilized by the addition of 70g of hydroquinone methyl ether, the solvent was removed at a temperature of 50°C and a pressure of 150 mm Hg in a thin layer evaporator until the residual content of the solvent was less than 0.1% .

The unsaturated resin according to this example was obtained with a yield of 95% and had the following characteristics:

Colour: yellow-brown

•Viscosity: 120 poise at 25°C

OH value: 24

Acid value: 7

Acrylic unsaturation: 7.5 mech./g

Example 13

The following materials were introduced into the apparatus described in Example 12:

22.60 kg dimer acid (EMPOL 1010, see Example 7)

16.32 kg of pentaerythritol

30.80 kg acrylic acid

20.00 kg of benzene

1.40 kg p-toluenesulfonic acid dissolved in 1 kg water 0.080 kg copper-(I)-oxide

0.020 kg of triphenyl phosphite

After an esterification reaction in lbpet of 8 1/2 hours, 9.8 kg of water had distilled.

The esterification solution was divided into two equal parts:

The first part (resin no. 13A) was purified as described in Example 12.

To the second portion (resin No. 13B) was added a mixture containing 3 kg of ethanol and 3 kg of benzene, the esterification was continued for 3 hours during which time 0.950 kg of water was distilled from, after which this second portion was then purified in the usual manner.

The two resins had the following characteristics:

Treatment with ethanol produced an transesterification which had the following effects: reduction of the chain length, resulting in a reduction of the viscosity, whereby a more homogeneous molecular weight distribution was obtained than for resin No. 13A, which was shown by comparison of the distribution curves of the molecular masses measured by chromatography with gel penetration, lowering of the acid number and a slight reduction of the acid number of acrylic unsaturation.

Example 14

.A resin was prepared as described in Example 12 but the esterification was stopped when the hyd rof y ltall et was 48.. After purification it had the following characteristics:

Viscosity: 60 poise at 25°C

OH value: 48

Acid value: 9

Acrylic unsaturation: 7.5 mech./g

One kg of this resin was placed in a 2-liter double-walled glass reactor equipped with a mechanical stirrer and a thermometer,

and 47 g of a mixture of 2,4- and 2,6-toluenediisocyanate and 1 g of triethylenediamine were added. The temperature was raised to 60°C with stirring for one hour. Filtration of the product then showed no presence of isocyanate. The reaction took place in air but the reactor was protected from water vapor by means of a silica gel column. The viscosity of the mass decreased progressively. The resin obtained had the following characteristics:

Viscosity: 395 poise at 25°C

OH value: 20

Acid value: 9

Acrylic unsaturation: 7.5 mech./g

Example 15

a) The following mixture was esterified in the reactor described in Example 12: 11.30 kg dimer acid (EMPOL 1038, same as in Example 6) 10.88 kg pentaerythritol

21.OO kg acrylic acid

10.60 kg of benzene

1.00 kg 67% aqueous solution of p-toluenesulfonic acid 0.04 kg copper oxide

0.017 kg triphenyl phosphite

The esterification took place over the course of five hours. The temperature eventually reached 102°C and 3.95 kg of water was collected. After purification, 3.4 kg of a product with the following characteristics was obtained:

Viscosity at 25°C : 50 pois

OH value: 84

Acid value: 7.8

Acrylic unsaturation: 8.6 mech./g

b) The viscosity of the product could be adjusted by urethanisation with different isocyanates. lOOO g of the product obtained in a) and

0.5 g of triethylenediamine was reacted with the amounts of diisocyanates listed in the following Table II. The mixture was heated to 70°C until there was no appearance of isocyanate groups, which took about 1 hour.

Example 16

A mixture of 100 parts of resin according to Example 1 and one part of azobisisobutyronitrile was poured onto a "Teflon" disk with a depth of 1 mm.

A sheet of 12 micron thick dioriented polyethylene terephthalate was placed in contact with the coating to protect it from air. The disc was placed in an oven at 80°C. After 25 minutes, curing was complete. The polymer was insoluble in the usual solvents. After extraction with methyl ethyl ketone in a Soxhlet apparatus, a residue of 96.4% was obtained.

Eczema gel .17

The following two mixtures were prepared from the resin in Example 5:

Mixture A: 10 parts of resin according to Example 5

0.3 parts of a 50% solution of benzoyl peroxide in dioctyl phthalate

0.02 parts of a paraffin with a melting point of 52 - 54°C Mixture B: 10 parts of the above resin

0.3 parts of a 10% solution of dimethyl-p-toluidine i

ybutyl acrylate

0.02 part of the paraffin indicated above

After a quick mixing of compositions A and B,

a 500 micron film applied to a glass plate using a hand applicator. After a few minutes, the reaction started at ambient temperature and the paraffin floated to the surface. After 15 minutes a hard, non-sticky film was obtained.

Example 18

A film of thickness 500 microns was cast onto a glass plate from the unsaturated resin of Example 7 to which 0.5% benzoin methyl ether had been added.

This glass plate was placed in a sealed box equipped with a window of a sheet of bioriented polyethylene terephthalate with a thickness of 12 microns. Air was flushed out by passing a stream of nitrogen over a period of 10 minutes, followed by irradiation with a Phillips HTQ-4 1000 Watt ultraviolet lamp placed at a distance of 25 cm.

After ultraviolet irradiation for one minute, the resin was completely cured (96.5% soluble in methyl ethyl ketone).

Example 19

A film of the unsaturated resin according to Example 8, with a thickness of 100 microns was poured onto a glass plate. This film was cured with electron beam irradiation under the following conditions:

Electron accelerator : BBC, 300 KeV, 50 mA

Dose rate: 10 Mrad/sec.

Irradiation in an inert atmosphere was obtained by controlling the surface with combustion gases.

The film cured completely (more than 98% soluble in methyl ethyl ketone) with a dose of 1 Mrad, which represents a linear speed of the film of 70 meters per second. minute.

Example 20 Formulation for road markings.

A paint was prepared from the following ingredients:

lOOO parts of unsaturated resin according to Example 13B

500 parts methyl methacrylate

22pois, it was saturated with oxygen and kept in a thin-walled polyethylene container. At the end of 3 and 6 months, the viscosity decreased to 25 and 32 poise respectively.

The same product, stored in a glass container with the exclusion of air after flushing with nitrogen, polymerized within 5 days (viscosity y 20,000 pois).

Four drops of the 22-poise mixture were applied to the threaded portion of a series of 10 mm standard bolts, which were then hand-threaded into a jam nut. After 30 minutes the connection could not be unscrewed and after three hours at 22°C an unlocking torque of 0.64 m/kg was measured.

Example 23 Metal varnish.

An ultraviolet varnish which can be applied to metal sheets was obtained by mixing:

70 parts of the unsaturated resin according to Example 8

27 parts Tercarol 1 triacrylate (TERCAROL 1 is a registered trademark for the addition product of 12 moles of propylene oxide and one mole of glycerol, with a molecular weight of about 1000)

3 deier 2-hydroxyethyl acrylate monomaleate

40 parts ethyl acrylate

5 parts diethylene glycol diacrylate

0.5 parts colloidal silica (AEROSIL 200 - Degussa)

1 part PA-520 polyethylene wax (Hoechst) and

3 parts of a mixture of benzoin butyl ether isomers (Trigonal-14; Noury-Lande).

A layer of 22 g per m 2 of the composition was applied to a dewaxed tin plate using a roller. The sheet was fast with a speed of 0.5 m per minute under an ultraviolet lamp of the Hanovia type, placed at right angles at a distance of 7.5 cm from the sheet and with a strength of 80 Watt per cm. The applied varnish became hard and non-adhesive (pencil hardness: 2H, 97% soluble in methyl ethyl ketone, cross-cut adhesion test equal to 100%).

Example 24 Preparation of an ultraviolet sealant suitable for application to cardboard

A sealant of the following composition was prepared in a Werner kneader:

40 parts of the unsaturated resin according to Example 13B

0.2 parts of a mixture of benzoin butyl ether isomers

(Trigonal-14, see Example 23)

5.0 parts micro talc extra

7.8 barium sulfate, and

47 parts calcium sulfate (Leichtspat FFF, from Harzer Gips-werke) .

This composition was applied to cardboard in a thickness of 2

150 g per m using a reverse roller.

After ultraviolet irradiation for a period of 36 seconds under a Philips HTQ4 lamp at a distance of 25 cm, the cardboard had a hard surface (Persoz hardness 120 seconds) and could be sanded.

Example 25 Lacquer ^varnish^.

A varnish that could be cured with an accelerated electron beam was prepared from the following ingredients:

70 parts of the unsaturated resin according to Example 8

27 parts 1,4-butanediol diacrylate

0.5 parts colloidal silica (AEROSIL 200 - DEGUSSA), and 2.5 parts silica (SYLOID 74 manufactured by Grace).

This varnish was applied to a glass plate in a layer with a thickness of 50 microns by means of a hand applicator. With a dose of 1 Mrad (irradiation conditions identical to those described in Example 19), the pencil hardness was equal to 5H and the product was unblemished

in methyl ethyl ketone to a degree of 96.9%.

Example 26 Paint.

A paint which can be applied by means of a carpet machine and which can be cured by an accelerated electron beam was prepared from the following ingredients: 15 parts of the unsaturated polyester as described below

20 parts of the unsaturated resin according to Example 13B

15 parts 1,4-butanediol acrylate

43 parts titanium oxide

4 parts Shepperd Brown 49 dye and

3 parts silica (SYLOID 74 manufactured by GRACE).

The unsaturated polyester used in this composition was prepared by condensation of a mixture of maleic anhydride, adipic acid, ethylene glycol, dipropylene glycol and 2-ethylhexyl alcohol in

1 a roolar ratio of 0.4 : 0.6 : 0.8 : 0.2 : 0.1.

This composition forms a very stable "carpet" without giving off any smell. It is applied in layers of 120 g per m on cardboard panels pre-treated with a primer and carefully sanded. Irradiation with an electron beam is carried out under the conditions used in Example 19. The dose required for complete curing is 2 Mrad, which represents a linear velocity of the film of 35 meters per second. minute. The appearance of the panels was excellent. The paint was glossy because it was very hard (pencil hardness: 3 H), water resistance and adhesive resistance were excellent and the appearance was unchanged after 500 hours in a Weather-O meter.

Example 27 Paint.

A paint which could be applied by means of a roller and which could be cured by means of an electron beam was prepared from the following ingredients:

20 parts of the unsaturated resin according to Example 12

12 parts of an unsaturated resin of the poly ether acrylate-urethane type described below 10 parts of an oligomer of Tercarol-1 triacrylate (described in Example 23)

12 parts 1,4-butanediol diacrylate

20 parts titanium oxide

22 parts chalk

3 parts silica (SYLOID 74), and

1 part colloidal silica (AEROSIL 200)

2

A coating of 52 g per m was applied by means of a roller to a rigid fiber board (60 x 30 cm) previously treated with a glycer-olphthalic acid transfer compound.

After irradiation under the conditions described in Example 19 (2 Mrad) and a linear velocity of 35 m per minute, a coating was obtained which had a glossy surface and a pencil hardness of 4 H.

The unsaturated resin of the polyetheracrylate-urethane type used in the composition according to this Example was prepared by

to react 3 mol of polypropylene glycol with 4 mol of isophorone diisocyanate and 2 mol of hydroxyethyl acrylate in the presence of 2 wt% (calculated on the basis of the diisocyanate) of triethylenediamine at 80°C for 10 hours, until the isocyanate bands in the infrared spectrum had disappeared.

Example 28

A mixture of :

68 parts of the product according to Example 12

27 parts trimethylolpropane triacrylate

2 parts acrylic acid, and

3 parts benzoin ethyl ether

was applied at a rate of o 3 g per m 2 using a reverse roller on the surface of a polyethylene film that had been treated with the corona effect. A film of aluminum was then applied to the coated surface.

The laminate was quickly placed under a Hanovia lamp (80 watt/cm) with the polyethylene surface facing the lamp, at a speed of 200 m per minute. minute. After an aging of 10 minutes, it was no longer possible to separate the two films without tearing pieces of aluminum foil.

Example 29 Offset ink for WEB PRESSE.

This was made from the following ingredients: 15 parts phthalocyanine blue (color index, pigment blue 15)

64 parts of the unsaturated resin according to Example 12

IO parts trimethylolpropane triacrylate

5 parts dioctyl phthalate

5 parts benzoinbutyl eth is , and

1 part polyethylene wax PA-520 (HOECHST)

This ink was applied to a thickness of 1 micron on a paper strip. It then became fast with variable speeds and with a distance of approx. 5 cm below a Hanovia No. 6525 A 431 ultraviolet lamp with a 62.5 cm arc length and a power of 5000 watts (quick blue lamp with medium pressure). Appearance of offset occurred at 4 m per second and the cured ink was unscratchable two hours after irradiation.

In the case of four-colour printing on a rotary press equipped with three lamps of the type described above, the ink was used at a rate of 310 m per minute.

Example 30 Offset ink_fqrotary presses^

An ink was prepared from the following ingredients:

15 parts phthalocyanin blue ( f argeind ex , pigment blue 15)

59 parts of the unsaturated resin according to Example 12

15 parts of the unsaturated resin according to Example 13B

5 parts diocty lf thai at

5 parts of a mixture of benzophenone and Michler's ketone in a weight ratio of 6:1, and

1 part by weight polyethylene wax PA-520 (HOECHST).

This ink had a reactivity similar to that of Example 29.

Example 31 Offset ink for sheet-fed machine is.

'An ink was produced from the following ingredients:

16 parts AAMX benzidine yellow (color index, pigment yellow 13)

70 parts of the unsaturated resin according to Example 6

4 parts trimethylolpropane triacrylate

5 parts dioctyl phthalate

4 parts of 1-phenyl-1,2-propanedione 2-[O-(benzoyl)oxime, and

1 part polyethylene wax PA-520 (HOECHST).

Appearance of offset was determined as described in Example 29 and occurred at 3.5 - 4 m per second.

In four-colour printing on a sheet-fed press equipped with three ultraviolet lamps per 80 watts per cm, it was possible to work at a speed of 8,000 sheets per hour.

Example 32 Offset ink for sheet-fed machine.

An ink was prepared from the following ingredients:

16 parts AAMX benziding yellow (color index, pigment yellow 13)

50 parts of the unsaturated resin according to Example 14

24 parts of the unsaturated resin according to Example 13B

5 parts dioctylf th alate

5 parts of a mixture of benzophenone and Michler's ketone in the weight ratio 6:1, and

1 part polyethylene wax PA-520

This ink had a reactivity similar to that of Example 31.

Example 33

Yellow UV-curable inks were prepared from the following ingredients: 16 parts of AAMX benziding yellow (color index, pigment yellow 13) 70 parts of one of the various binders listed in Table III

4 parts trimethylolpropane triacrylate

4 parts dioctyl phthalate

5 parts of a mixture of benzophenone and Michler<*>'s ketone in a weight ratio of 6:1, and

1 part polyethylene wax PA-520

Appearance of offset was determined as described in Example 29.

Example 34

In the yellow ink according to Example 33 produced with binder according to Example 15 a (non-urethanized), 4 parts of methylolpropane triacrylate and 4 parts of dioctyl phthalate were replaced with 8 parts of N-methyldiethanolamine diacrylate.

Offset appeared at 3.25 m/second (bending of 1 m/second).

Example 35 Flexographic ink.

This was made from the following ingredients:

6 parts phthalocyanin blue (color index, pigment blue 15)

45 parts of the unsaturated resin according to Example 13B

30 parts 1,4-butanediol diacrylate

10 parts N-methyl-diethanolamine-diacrylate

8 parts of a mixture of benzophenone and Michler's ketone in the weight ratio 6:1, and in

1 part polyethylene wax PA-520

Offset determined as in Example 29 appeared at 1.75 m/second.

Application of 5 micron films was carried out with a stick applicator on the following substrates:

nitrocellulose lacquered aluminum foil

nitrocellulose varnished Cellophane MS

Polyvinylidene chloride (lubrication) lacquered Cellophane XS1 Polyvinylidene chloride (emulsion) lacquered Cellophane XS2 Polyethylene treated with corona effect

Use under a UV lamp (as described in Example 29) is satisfactory at more than 180 m per minute. There is no offset between print and substrate, nor print to print iclebing. The film is brilliant. Adhesion as determined by tape test is satisfactory and nail scratch resistance and rubbing resistance are good.

Example_36 White_offset-ink_for_raetal decoration.

This had the following composition:

55 parts surface-treated rutile titanium oxide

35 parts of the unsaturated resin prepared according to Example 15b2

2 parts dioctyl phthalate

8 parts of a mixture of benzophenone and Michler<*>'s ketone

in the weight ratio 6:1

The printing was carried out on an offset press for thin plate debridement. The treatment took place using three UV lamps, with medium mercury vapor pressure, air-cooled and at 80 watts per cm arc length. The printing speed was 5,000 sheets per hour. The wear and adhesion properties allowed stacking, storage, handling of the iron sheet stacks and reception for the application of colors and varnishes, which effected the subsequent color printing and varnishing of the thin sheets.

Claims (14)

1. Composition that can be polymerized by irradiation, characterized in that it comprises or contains as polymerizable binder(s) at least one compound with multiple acrylic radicals whose average composition corresponds to the general formula: where X is the radical derived by removing the OH groups from car- the boxyl groups of an organic carboxylic acid containing n COOH groups, and where the number of carbon atoms is between 14 and 90, preferably between 18 and 54, Y is the radical derived by removing the n - p hydrogen atom more from the hydroxyl groups of an organic compound containing m OH groups, Z is the monovalent radical derived by removal The OH groups from the carboxyl group of a monocarboxylic acid with at least one CH2 =CH -COO- terminal radical, n is an integer from 1 to 6, preferably from 1 to 4, m is an integer from 2 to 8, preferably from 3 to 6, p is a number from 0 to 2.5, provided that m-p-1 is a positive number other than zero, and that n(m-p-1) is between 2 and 15, or (b) an isocyanate-modified compound thereof. 2. Composition according to claim 1, characterized in that X in formula I is the radical derived from an organic aliphatic monocarboxylic acid. 3. Composition according to claim 1, characterized in that X in formula I is the radical derived from an organic polycarboxylic acid. 4. Composition according to claim 1, characterized by a1 X in formula I, the radical is derived from a mixture of at least 25 mol% of an organic carboxylic acid with from 14 to 90 carbon atoms and a maximum of 75 mol% of at least one organic aliphatic, c.cyclo- aliphatic or aromatic carboxyls with less than 14 carbons atoms. 5. Composition according to any one of claims 1-4, characterized in that Y in formula I is the radical derived from an organic compound selected from the group consisting of an aliphatic polyhydric alcohol, an oxyalkylated aliphatic polyhydric alcohol, a polyester alcohol, a polyether alcohol, an oxyalkylated polyester alcohol and an oxyalkylated polyether alcohol. 6. Composition according to any one of claims 1-5, characterized in that Z in formula I is the radical derived from a monocarboxylic acid selected from the group consisting of acrylic acid, an ester of one mole of a hydroxyalkyl acrylate with one mole of a dicarboxylic acid or anhydride, an ester of two moles of a hydroxyalkyl acrylate with one mole of a monocarboxylic acid or anhydride, and an ester of 3 moles of a hydroxyalkyl acrylate with one mole of a tetracarboxylic acid or anhydride, the alkyl radical in the hydroxyalkyl acrylate having 2 to 12 carbon atoms. 7. Composition according to any one of claims 1-6, characterized in that the isocyanate is selected from the group consisting of aliphatic, cycloaliphatic, heterocyclic and aromatic mono- and di-isocyanates and the addition products of these diisocyanates with monoalcohol groups. 8. Composition according to any one of claims 1-7, characterized in that the polymerizable binder also contains at least one compound selected from the group consisting of copolymerizable reactive unsaturated polymers, copolymerizable unsaturated oligomers and copolymerizable unsaturated monomers. 9. Composition according to any one of claims 1-8, characterized in that it comprises 10 - 90% by weight of the polymerizable binder and 1 - 15% by weight of at least one photochemically active compound selected from photoinitiators and photosensitive components. 10. Composition according to any a <y> claim 1-9, characterized in that it. also contains up to 40% by weight of inert polymers and/or plasticizers. 11. Composition according to any one of claims 1 - 10, characterized in that it also contains up to 60% by weight of pigments and/or fillers. 12. Composition according to any one of claims 1 - 11, characterized in that it also contains 1-10% by weight of conventional additives for paints, varnishes, coatings, adhesives or inks. 13. Paints, varnishes, coatings or adhesives which can be cured by irradiation, characterized in that they comprise a composition according to any one of claims 1-12. 14. Printing inks or varnishes, especially offset inks, which are hardenable - By irradiation with ultraviolet light, characterized in that they comprise a composition according to any one of claims 1 - 12.