SE427465B - Meltable polyacrylate dispersion and process for its use - Google Patents

Abstract

It has been found that pastes of particulate polymers dispersed in a soft resin phase can be prepared and can then be made to harden by melting the thermoplastic binder. Polymers of the type of polystyrene and polyacrylate are particularly suitable for this purpose. When combined with a pigment or another colouring matter, these compositions can be used as printing inks, while in the absence of any colouring matter, they can be used as clear surface coating materials.

Description

79014614-0 10 15: 20 äs 30 35 or similar hardens by oxidation and / or polymerization sation. _ Although it is necessary to ink quickly and can be conveniently made to cure after printing, is it is equally necessary that it does not harden or dry in the press. Inks containing volatile components can thicken in the press as the solvent evaporates, it becomes difficult or impossible to master the printing process.

Air oxidizing varnishes, drying oils or the like may thicken or stick to the press when it comes in contact with air. Such inks are particularly prone to form "leather", when the press is switched off during a run. A pressure color, which is not prone to such changes in printing the press, is said to remain "open". in The ink techniques have tried to produce paints, which can be dried quickly and with low energy supply for triggering the hardening, which does not emit pollutants materials to the air, which remain open in the press and which at the same time satisfies the physical process of the printing process and mechanical receivables. Great attention has been focused on chemically highly reactive compositions. After printing these inks harden by polymerization and / or crosslinking, which is triggered by heating or irradiation.

A typical chemically reactive system contains polyfunctional tional acrylic acid esters (often in combination with others unsaturated materials), one or more ultraviolet initiators, pigments and several secondary components for position of the physical properties of the paint (see American patents 3,8OU_6U0 and 3,881,942). In normal use Invoices are printed with such inks in presses equipped with ultraviolet lamps, for which the film on paper or other material is exposed immediately after printing ningen. The inks dry quickly and essentially without release of polluting materials. Inks based on such highly reactive materials has, however, limited storage capacity. Acrylates and others commonly used reactive materials have been found to be chemically incompatible 10 15 20 25 30 35 . based on polyvinyl chloride plastisols are described in U.S. Pat. No. 3,760,724. 3 with certain pigments, which are suitable in printing inks. The contents carries risks of poisoning or is dangerous eye irritant substances, and they are often irritating to the skin. When the inks are off- seen to be dried by ultraviolet-initiated reaction, involves the ultraviolet radiation itself and those for operation of the ultraviolet lamps necessary high voltages health and safety risks.

U.S. Patent No. 3 OZU 213 discloses a in heat-drying paint carriers based on polyvinyl chloride plastisol, more specifically finely divided polyvinyl chloride dispersed in a liquid plasticizer, which has low viscosity and whose solubility parameters are carefully adjusted to polyvinyl chloride, and containing a compatible thermo- plastic resinous binder for increasing the ink In cohesion and stapling. Improvements to inks and vinyl chloride copolymer These inks are dried by the application of heat, which bringar.de liquid plasticizers and polyvinyl chloride or the vinyl chloride copolymer to dissolve in each other.

These inks based on polyvinyl chloride plastic insoles can thus be easily dried in heat without significant release of liquid materials to the atmosphere, These inks however, does not have good properties in the printing presses. O- appropriate accumulation of material on the printing screen in lithographic Offset presses occur when polyvinyl chloride plastisol ~ containing inks are used. Furthermore, both require them specified patents use of at least one plasticizer in the polyvinyl chloride plastisol paints. These plasticizers may, as set forth in U.S. Pat. ten 3 02k 213 damage natural rubber rollers in the printing presses. MAN must therefore use polyurethane rubber paint rollers or other plasticizer resistant materials.

The present invention provides non-volatile, i heat hardening paste. It has been shown that pastors of particulate thermoplastic polymers dispersed in a soft resin phase can be produced, which hardens in heat through 7904514-0 790lr61lr-Û 10 15: 20 -25 30 35 fusion of the thermoplastic binder. Pigmented or colored otherwise, these preparations have use as inks. Uncoloured, they can be used as clear coatings over printed matter. In addition, these have fusible pastors use as special coatings and adhesives and can produced in self-supporting forms.

According to the invention include non-volatile, in heat curing hardeners in paste form for inks individual solids particles of glassy thermoplastic polymeric material, which polymeric material is made of at least 51 percent of at least one monomer selected from monomers of acrylic which poly- about s0 ° c individual a staple softening acid type and aromatic monovinylidene monomers, more material has a glass transition point of at least and a particle diameter of 0.05 -'50 μm, which particles of polymeric material are dispersed in promotion, cohesion-enhancing materials, whose point is at or below room temperature, which material and which cohesion-enhancing material is available being in the composition in a ratio of polymeric material / cohesion increasing material from about 1: 5 to about 1: 1.

The cohesion-increasing material may be a resin or a resin mixture, the softening point of the cross is at or below room temperature or has been lowered by dilution with an oil.

The binders used according to the invention are particulate thermoplastic polymers with a molecular weight over about_50,000 and a glass transition temperature of about 5000. Suitable polymers may be based on one or several monomers which can undergo addition polymerization.

Typical preferred polymers which can be used according to The invention includes polystyrene type polymers or polyacrylic acid type.

The particle size of the binder is not decisive meaning, but for lithographic inks or letterpress colors, particles of about 0.05 - 2 μm in transverse cut. Particles of about 0.5 μm in cross section are most suitable.

For stencil printing, much thicker color films are applied, 10 15 20 25 30 35 7904614-0 5 why larger particles can be tolerated; such high particulate sizes of about 50 μm can be used with coarse stencils. cloths and thick color films. '_ The polymers used in the pastes according to the invention The polystyrene type is based on addition polymers. monomers, which include styrene, alkyl substituents styrene or other aromatic monovinylidene monomers, either alone or in association with one or more monomers, with at least 51 percent of the monomers being constituted of one or more of the following monomers: styrene, alkyl substituted styrene or aromatic monovinylidene.

Polystyrene-type thermoplastic polymer particles of a size useful for the present invention may be obtained by evaporating water from dispersions, produced thereon in U.S. Pat 3,853,579 described method. Alternatively, the particles can produced by crushing or grinding suitable moplastic polymers, by controlled precipitation from solution or by high shear dispersion of molten polymer in a non-solvent and subsequent cooling and drying ning. In many cases, a classification procedure may be necessary necessary to obtain the optimum particle size for the material. _ The thermoplastic polymer particles of polystyrene type, which are useful in these pastors, were prepared by aromatic monovinylidene monomers alone or in combination tion with one or more comonomers. With "aromatic mono- vinylidene monomer "is meant to form an aromatic ring in each molecule of the monomer is bound to a radical by the formula wherein R represents hydrogen, lower alkyl (eg alkyl having 1 - U carbon atoms such as methyl, ethyl, n-propyl, n-butyl and isobutyl).

Examples of these aromatic monovinylidene monomers are 'EY9Û461Åf-O 10 15 20 25 30 35 6 styrene, α-methylstyrene, ar-methylstyrene, ar-methoxystyrene, ar-hydroxymethylstyrene, ar-butylstyrene, ar, ar-dimethylstyrene styrene, ar-chlorostyrene, ar¿adichlorostyrene and ar-ethylstyrene.

Comonomers with the above-mentioned aro- The monovinylidene monomers may comprise one or more several addition polymerizable compounds, e.g. saturated esters of ethylenically unsaturated carboxylic acids, including monomers of the acrylic acid type, which group includes acrylates, acrylates, acrylonitrile and methacrylonitrile, such as methyl methacrylate; ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylates and the like; ethylenically unsaturated esters of boxyl acids, such as vinyl benzoate, vinyl toluate and the like; and other copolymerizable vinyl and conjugated ali-D phatic diene monomers.

Monomers, which tend to increase the polymer film-forming properties, may be added, but not in such to the extent that the polymer tends to melt during conditions for pasta production by lowering the glass the transition temperature below about 5000. Examples of such monomers are 1,3-butadiene, isoprene, lauryl methacrylate and stearyl methacrylate.

Other comonomers may be included, provided they do not interfere with tion according to the invention. It may be appropriate to include introduce certain additional monomer components in order to facilitate the production of particles of suitable size. The U.S. Pat. No. 3,853,579 discloses the addition of up to 25% by weight of ethylenically unsaturated carboxylic acids, which obviously contributes to the stabilization of the dispersion during aqueous phase polymerization. Such monomers can be used in the thermoplastic polymers of present with heat-digestible pastes. These are ethylenically unsaturated carboxylic acids can be mono- or polycarboxylic acids. acids, eg acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid and maleic anhydride, citraconic acid and citraconic anhydride and other similar acids.

The preferred thermoplastic polymers of poly- 10 15 ' - which are appropriate constituents of the 20 m 30 35 7904614-0 7 type of styrene, which are useful in the present pastor, made from at least 51 percent aromatic monovinylidene monomer, preferably styrene, c-methylstyrene, p-methylstyrene and / or chlorostyren. Preferred comonomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, iso- butyl methacrylate, lauryl methacrylate, stearyl methacrylate, acrylonitrile and 1,3-butadiene.

The pastes used in the pastes of the present invention The polyacrylate type polymers are based on acrylic monomers such as alkyl acrylates, alkyl methacrylates, acrylic nitrile and methacrylonitrile either alone or in combination with one or more copolymers, with at least 51 percent of the monomers are one or more of the given the acrylic monomers. Alkyl acrylate and methacrylate mono- the pastoral thermoplastic polymers of poly- acrylate type, includes methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate lat, butyl methacrylate and isobutyl methacrylate. Of those specified The acrylate type monomers are methyl methacrylate and acrylate. nitrile preferred. ir In Comonomers other than acrylic monomers, which may be reversed, includes one or more of the foregoing described aromatic monovinylidene monomers, others saturated esters of ethylenically unsaturated carboxylic acids, ethylenically unsaturated esters of carboxylic acids and other compounds polymerizable vinyl and conjugated aliphatic diene mono- more as described above. Other samono- may be included if they do not interfere with the operation of the invention, eg comonomers added to contribute to stabilization during emulsion polymerization.

Polyacrylate-type thermoplastic polymer particles with a size suitable for the invention can be conveniently obtained by evaporation of the diluent from the emulsion or dispersion polymerizing systems as set forth in Dispersion Polymerization In Organic Media, edited by 79c4s1ß-o 1D 15 ' Resins that can be used are hydrocarbon resins, including 20 25 30 35 8 K.E.J. Barrett (John Wiley & Sons, NY, 1975). Alternatively particles can be produced by grinding or grinding the polymers, by controlled precipitation from solution. In many In this case, particle size classification may be necessary to keeping the optimal size for the material.

The coherent soft resin phase of the paste is stands for a staple-promoting, cohesion-enhancing material, which may be a resin or a resin mixture, the soft is at a temperature at or below room temperature or which has been diluted with an oil for a suitable lowering softening point. The term "resin" is used herein. limited to amorphous organic solids, semi-solids and viscous liquids with a viscosity above about 2000 cP at room temperature; Such resins are usually polymeric, however the number average molecular weight must be below about 5000. Typical naturally occurring coal tar and other fossil resins synthetic aliphatic and aromatic hydrocarbon resins made from petroleum - derived raw materials or hard coal, and resins based on pure hydrocarbon monomers and anomer combinations, such as styrene and alkyl substituted styrenes, indene and dicyclopentadiene, terpene resins, rosin nium and rosin esters, such as hydrogenated methyl ester of rosin and phenolic resin modified pentaerythritol ester of rosin, thermoplastic ketone-formaldehyde resins, thermoplastic resins of condensed ketones, resins based on acrylic acid esters and alkyl-substituted acrylic acid esters and transesterification products of alcohols with di- methyl terephthalate process esters.

Diluent oils can be aliphatic, aromatic or naphthenic in nature and may contain polar functionality, but must be compatible with and resolved in the resin system. Typically, they have solubility parameters in between about 7.0 and 8.5. They must be essentially non-volatile at the temperature at which the ink is dried, typically 150 ° C or higher. It is important to choose diluents, which do not rapidly solvates the particulate thermoplastic phase 10 15 ' of the kind typically used in the manufacture of 20 25 30 35 79014614-0 9 at room temperature. This can be achieved by avoiding the diluent oils, which closely resemble the particulate matter the solubility parameter of the thermoplastic. Typically, the center point for the solubility parameter of ~ polystyrene with respect to weak hydrogen bonded solvents, such as hydrocarbon oils or chlorinated hydrocarbons, at or about 9.3, and with respect to moderately hydrogen-bonded solvents such as esters or ketones, it is at or about 9.0. Polystyrene is insoluble in strongly hydrogen-bonded solvents. The center of the solution the similarity parameter for poly (methyl methacrylate) with respect to on weakly hydrogen bonded solvents such as hydrocarbon oils and chlorinated hydrocarbons are typically about 10.8, and with respect on moderately hydrogen-bonded solvents such as esters or the ketone is about 10.9. Poly (methyl methacrylate) is insoluble in strongly hydrogen bonded solvents. Liquid plasticizer polyvinyl chloride plastisols (commonly referred to as "primary" plasticizers ") such as those described in U.S. Pat patent specification 3 02ä 213, has solubility parameters between about 8.5 and il and is not used in pastors according to the finding. : _ There are no such restrictions for themselves the solubility parameter of the resin. Solvation is so long- sam, that also inks containing resins, as close corresponds to the solubility of the particulate thermoplastic parameter, can be produced and used in a press. I ex- In three cases, solvation can proceed at such a rate. that certain combinations of resin and thermoplastic polymers will be limited to applications where colors are prepared as needed and stored for a maximum of about one day. In larger printers, inks are usually prepared because they are needed. Under these circumstances, they can the particulate thermoplastic polymers and the resin have essentially the same chemical composition and differ from each other only in physical form and molecular weight, for example polystyrene particles, which are dispersed in a soft resin phase consisting partly of polystyrene resin. '79 Û461h-Û 10 15. 20 25 30 35 10 The thermoplastic polymer and the soft resin according to the invention should preferably be used in such proportions, that fi the ratio of polymer to resin is preferably between about 1: 6 and about 1: 1. Further the ratio of soft resin to diluent oil may vary from such cases where the preparation is oil-free (ie the soft the resin of nature is thin enough to give the desired rheology of the finished digestible paste), to a ratio of about 1:15 between resin and oil.

Q The primary mechanism by which the pastes according to the invention dries, appears to consist in the shaped thermoplastic binder when heating the paste melts into a coherent film in which the soft resin the phase is largely loose and / or enclosed. In some In this case, it may be desirable for the paste film to harden further. ligare. This can be achieved by using the soft resin phase choose in whole or in part materials that may undergo ' polymerization or crosslinking during the thermal convergence the melting of the particulate thermoplastic material or thereafter In such cases it may be advantageous to add suitable catalysts, desiccants, accelerators or other additives, which are necessary or desirable for initiation_or promotion of the desired the polymerization or crosslinking reaction. This post- curing of the heat-dried pasta film can be achieved by incorporating one or more unsaturated alkyd resins in the resin phase, such as alkyds based on phthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid talic acid, hydrophthalic acid, maleic acid, fumaric acid or benzoic acid acid or their anhydrides and modified with unsaturated fatty acids, rosin-modified alkyds, phenolically modified alkyds, epoxyalkyds, polyamide alkyds, isocyanate alkyds, and alkyds modified with styrene or substituted modified styrenes, such as styrene and acrylonitrile modified alkyds. The unsaturated isophthalic acid alkyds are preferred.

Similarly, drying or semi-drying oils, such as such as linseed oil, Chinese wood oil, oiticica oil, dehydrating 10 1s_ 20 25 30 35 790læ61¿r * -Û 11. castor oil, soybean oil, safflower oil, fish oil or pine oil, used as a hardener in the resin phase. These oils can be used in its natural state or can be thickened for increase in viscosity by heating or other partial polymerization. J When such polymerization-drying materials_ included in the paste, appropriate desiccants or catalysts, which promote oxidative crosslinking and merisation, for example salts or complexes of metals, which may exist in more than one valence stage, such as vanadium ociacetylacetonate, vanadinoxy sulfate, vanadinoxy-1,1,1-tri- fluoroacetylacetonate, vanadinoxy-1-phenylacetylacetonate, iron (III) acetylacetonate benzoin, manganese octoate, lead naphthenate, cobalt (III) acetylacetonate, titanylacetylacetonate, cobalt (III) - naphthenate, cobalt (II) -2-ethylhexanoate, cobalt (II) stearate, cobalt (III) stearate, cobalt (II) acetylacetonate, manganese (II) - stearate, manganese (III) stearate, manganese (II) acetylacetonate, man- (III) acetylacetonate, manganese naphthenate, zirconium acetylate acetonate, vanadyl naphthenate, ferrous sulfate, ferrous phosphorophosphate barrels, ferrous sulfide, ferrous (II) complex of ethylenedinitrile tetraacetic acid, iron (II) -o-phenanthroline, iron (II) hexacyano- ferrate (II), ferrous acetylacetonate and the corresponding nickel, copper, mercury and chromium.

In addition to the essential features described above, the constituents may be surfactants, dispersing aids for pigments, waxes, lubricants, tackifiers and the like are added when the pastes are used in inks.

The use of a coloring additive is not making of the invention. The digestible solid dispersions can be used unpigmented as clear overprint varnishes.

When a one-color additive is desired, it may be a pigment or a dye. The coloring additive is dispersed preferably in the soft resin phase of the ink. It can, however in some cases it may be appropriate to incorporate the coloring the batch in the particulate thermoplastic material.

When used as printing inks, the pastes can according to the invention is used in all kinds of printing processes that require a pasty color. Ordinary printing processes where pasty Inks used are letterpress, lithography and stencil printing.

The printing press can be fed with sheets or webs, and the printing 7904614-o 10 15 20 25 30 35 12 can be made of paper, cardboard, fabric, metal, glass, plastic, wood, leather, rubber or other surfaces. Variations in pressure the rheology and adhesion properties of the paint are required for timal results and each selected printing process and each selected basis. Inks based on pastes according to the invention can be prepared to meet the specific requirements by appropriate selection of the materials used in the resin phase and their relative concentrations. This will be appreciated by men in the field of ink preparation.

Except by printing, the pastes can be applied to the substrate by roller coating, squeegeeing, stenciling, dipping or the like, in particular for the manufacture of special coatings or for use as thermosetting adhesives. Self-supporting molds can be produced by molding, dip forming, rotational forming, shell forming and the like.

. In order to obtain optimal results with a given manufacturing variations of the paste's rheology and adhesion properties. The pastes can be prepared so that they fill these requirements by appropriate choice of those in the resin phase invert the materials and their relative concentrations. This easily understood by those skilled in the art After printing, coating or molding can the pastes according to the invention are dried by heating to at least about 75 ° C, preferably at least about 150 ° C, so that the particulate, glassy thermoplastic resin melts together. This can be done in such a conventional dryer. oven with forced draft, which is usually used in pressure rier. Since no air flow is required for removal obtaining volatile material, however, it is often advantageous to heat the pasta film by irradiation, typically in the infrared range. At 150 ° C the pasta can be melted by heating for about 0.01 s to about 2 minutes, wherein longer time is required for pastors who do not contain than for those containing pigments. The heating time may also vary with the thickness of the pasta coating, the nature of the team and the purpose for which the pasta is used (eg glue or molding material). 10 1st 20 25 30 79046H-0 13 Example 1 Finely divided polystyrene with a particle size of on average about 0.5 μm and with a molecular weight of about 1,000,000 is obtained by evaporating the water at room temperature from a commercially available polystyrene dispersion sold for use as a coating pigment for paper. The soft resin phase and the dilution phase of the the paint was combined with the polystyrene and pigments with grinding of a mill; Hoover Automatic Muller, for obtaining of a corpse-like pasta. The final composition is: Weight parts 100 Ingredients Polystyrene Hydrocarbon resin, mainly aromatic, based on monomers. from petroleum and coal, point (ring and ball) 10 C, number average molecular weight below 5000 260 In Extrude oil, from 40 petroleum, solubility parameters about 7.8, volatility less than ø, 1% at 150 c.

Carbon black I 40 I The color is used for printing on paper in a graphic offset printing. The printed sheets are guided with about H5 m / min under a 100 W / cm infrared lamp with maximum power at about 1 μm (line heater model 5193-5 made of Research Incorporated, Minneapolis, Minnesota, USA, driven at 230 V) at a distance of 25 mm from the lamp reflector edge, leading to rapid printing of the ink film.

Thereafter, the ink is dry and smudge-free.

Example 2 5 An ink of the following composition is prepared on the procedure set forth in Example 1. 7904614-0 10 15 ' Example 1. The preparation is identical to that of Example 1 20 25 30 35 14 Weight parts 100 Ingredients Polystyrene Hydrocarbon resin, mainly aro- mathematically, based on monomers from petroleum and coal, point (ring and ball) 10 C, number average molecular weight below 5000 Varnish, phenolically modified penta- erythritol ester of rosin dissolved in alkali-refined linseed oil with soluble about 7; 8, weight ratio holding U0: 60, volatility below 0.1% at 200 ° C; 100 Carbon black 36 The paint used for printing and dried as in Example 1. After drying, the ink is dry and smudge-free.

Example 3 An ink was prepared in the same manner as in 160 except that a polystyrene having an average particle size of ÛQS - 0.8 μm and having a molecular weight of about 1,000,000 was used, which polystyrene was obtained by evaporation of the water at room temperature from a commercially available polystyrene dispersion, which is sold for use as a laying pigments for paper. The paint is printed and cured so as in example 1. Thereafter, the ink is dry and smudge-free.

Example H I An ink was prepared as in Example 1. the preparation is identical to that of Example 1 except that one polystyrene_with an average molecular size of about 0.2 μm and a molecular weight of about 1,000,000 was used, which styrene was obtained by evaporating the water at room temperature. of a commercially available polystyrene dispersion, which sold as a pigment for paper coating. The printing ink pressed and cured as in Example 1. Thereafter, the the color is dry and smudge-free.

Example 5 An ink was produced in the same manner as in Example 1. The final composition is as follows. 10 15 20 25 790lf614-0 15 Ingredients Weight components Polystyrene 100 Hydrocarbon resin, based mainly on u-methylstyrene and styrene; mjuä- melting point (ring and sphere) 25 C; number average molecular weight below 5000 160 Extension oil, derived from petroleum, solubility parameters about 7¿8, volatility less than 0.1% at 150 C¿ 80 'su Carbon black The paint is used for printing and dried as in Example 1. Thereafter, the paint is dry and smudge-free.

Example 6 An ink was prepared in the same manner as in Example 1 with the following composition.

Ingredients Weight components Polystyrene 100 Hydrocarbon resin, mainly aliphatic, based on monomers from petroleum, softening point (ring and ball), 10 C, number average molecular weight below 5000 160 Extension oil, derived from petroleum, solubility parameters about 7¿8, volatility below 0.1% at 150 DEG C. 50 31 Carbon black The ink is used for printing and is thus dried as in example 1. Thereafter, the ink is dry and smudge-free.

Example 7 An ink is produced in the same way as in the example 1 with the following composition. §É§ÉÉEɧÉÉlÉÉ_ Weight parts Polystyrene 100 Methyl ester of rosin with a viscosity of about 2700 CP 150 Varnish, phenolically modified penta- erythritol ester of rosin dissolved in alkali-refined linseed oil with soluble about 7.8, weight ratio sloping U0: 60, humidity below 0.1% at 1000 ° C. 100 Carbon black '30 7904614-o 10 15 20 25 30 35 16 The ink is used for printing and dried as in Example 1. Thereafter, the ink is dry and smudge-free.

Example 8: An ink is produced in the same way as in the example 1 with the following composition.

Ingredients Weight components Polystyrene 100 Hydrocarbon resin, mainly aromatic, based on monomers from petroleum and coal, softening point (ring and sphere) .1D ° C, number average molecular weight under 5000. 160 Varnish, phenol modified, penta- erythritol ester of rosin dissolved in linseed oil isophthalic acid alkyd with high oil quota, weight ratio 20:80, - - volatile below 0.1% at 50 ° C. 100 Carbon black _-: - H0 The paint is used for printing and dried on the same _like in example 1.-Then the paint is dry and smudge-free.

Example 9 An ink is produced in the same way as in the example 1 with the following composition.

Ingredients _ / Weight components Polystyrene '100 Hydrocarbon resin, mainly aromatic, based on petroleum monomers and hard coal, softening point (ring and ball) 10 ° C, number average molecular weight below 5000. 80 Hydrocarbon resin, mainly aromatic, based on monomers from petroleum and hard coal, softening point (ring and ball) 2s ° c. ; no Fluorescent chart pigments (Hercules Incorporated) '95 The paint is used for printing and dried on the same as in Example 1. Thereafter, the paint is dry and smudge-free. Example 10 7, An ink is produced in the same way as in the example 1 with the following composition. 10 15 20 25 30 35 17 Ingredients Weight components Polystyrene 100 Hydrocarbon resin, mainly aromatic, based on petroleum monomers and hard coal, softening point (ring and ball) 10 ° C, number average molecular weight below 5000. 180 Crude oil, derived from petroleum, solubility parameters of about 7.8, volatile hot below 0.1% at 150 ° Q, 20 Titanium dioxide _. 7 15 _ The paint is applied by stencil printing on glass and dried by heating in an oven at 135 ° C for 2 minutes.

The resulting film is dry and scratch resistant.

Example 11 The ink of Example 1 is applied by stone cil print on cotton fabric. The ink is solidified by infrared irradiation as in Example 1. - The fabric is washed in an automatic washing machine with detergent without loss of image.

Example 12 A paste of the following composition was prepared in the same way as in Example 1.

Weight parts 120 Ingredients, Polystyrene Hydrocarbon resin, mainly aromatic, based on petroleum monomers and hard coal, softening point (ring and ball) 10 ° C number average molecular weight below 5000.

Varnish, phenol-modified adenerythritol ester of rosin dissolved in alkali refined linseed oil with a solubility parameter of approximately 7.8, weight ratio 40:60 volatility below 0.1 few at 200 ° C. '100 The paste is applied as an overpressure varnish in a litho- 160 graphic offset pressure. The printed sheets are heated at 200 ° C for 2 minutes in a forced oven. Thereafter, the dry and smudge-free. §Xempe1 13 A paste of the following composition is prepared on the same as in Example 1. 7904614-o 7904614-0 10 15 20 25 30 35 'and was heated by being conducted under an infrared lamp, 18 Ingredients Weight components Polystyrene in I 100 Hydrocarbon resin, mainly aromatic, based on petroleum monomers' and coal, softening point (ring and sphere) 10 ° c, average molecular weight subp 5000. _ 0 100 Varnish, phenol-modified pentaerythritol ester of rosin dissolved in alkali refined linseed oil with solubility parameters approx 7.8, weight ratio 40:60, volatility below 0.1% at 0 ° C. so Crude oil, derived from petroleum, solubility parameter about 7.8, volatility below 0.1% at 50 ° C1. 0 20 0 Titanium dioxide '' lä The paste was applied to paper by roller coating which leads to rapid hardening of the pasta film. Then there is C coating dry and smudge-free.

Example 14 A paste of the following composition was prepared in the same way as in Example 1. _ Weight parts Polystyrene r - 100 Hydrocarbon resin, mainly aliphatic, based on monomers from petroleum, soft- point (ring and ball) 1000, number average molecular weight below 5000. 160 The paste is applied to a cold-rolled steel plate, Bonderit 100, by leaf coating. The coated plate heat at 175 ° C for 5 minutes in a forced oven.

Thereafter, the coating is dry and abrasion resistant. Example 15 The paste from Example 1 # is applied to two pieces bleached poplin by squeegee coating. The coated fabric is pressed together with an iron at 120 ° C for 1 minute. After cooling a strong bond between the fabrics is obtained.

Example 16 The paste of Example 14 is pressed into a metal mold, Ingredients which had previously been coated with a mold release agent. The The filled mold is then placed in an oven at 200 ° C below 10 ° C 10 15 ' 20 25 30 35 7904614-'0 19 minutes. After cooling, the resulting casting is removed the mold, which cast iron is an exact copy of the mold.

Example 1% - 22 Copolymers having the following composition are prepared by emulsion polymerization. The particle size of the polymer is about 0.5 μm and the molecular weight is about 500,000.

Approximate glass transition temperature Example Comonomer ratio, ° C 17 Styrene 60% 100 Methyl methacrylate H0% 18 Styrene 90% 100 ~ Methyl methacrylate 10% 19 Styrene 95% 90 Ethyl acrylate in% Styrene 95% 85 Lauryl methacrylate 5% 21 Styrene 90% 85 Methyl methacrylate 5% Lauryl methacrylate 5% 22 Styrene 70% 100 Acrylonitrile 30% The particulate thermoplastic polymers are clay by stripping the water from the emulsions.

Inks were made from each of these on the same methods as in Example 1 using the following setting.

Ingredients Weight components Particulate polymer '100 Hydrocarbon resin, mainly aromatic based on petroleum monomers and hard coal, softening point (ring and ball) 1000, number average molecular weight below 5000. 260 Crude oil, derived from petroleum, solubility parameter about 7.8, volatility below 0.1% at 15 ° C. now Carbon black H0 The ink is used for printing and dried as in Example 1. After drying, the ink is dry and smudge-free. ÉëÉERÉl_ÉÃ_ 1 An ink of the following composition is prepared in the same way as in Example 1. 7904614-0 10 15 20 25 30 35 20 Ingredients Weight components' Polystyrene _ 100 Resins, transesterification products of 2-ethyl- hexanol with dimethyl terephthalate process ether pillars consisting mainly of methyl and benzyl esters of biphenyldicarboxylic acids and tricarboxylic acids, viscosity above 2000 oP, number average molecular weight below 5000. 160 Carbon black _ - 26 The color is used for printing in a lithographic press and in a Van der Cook deduction press, and the prints dried by being conducted under an infrared lamp, as is written in example 1. Thereafter, the paint is dry and smudge-free.

Example 2U A digestible pressure paste is prepared with the following composition.

Ingredients Weight components Polystyrene 100 Hydrogenated methyl ester of rosin, viscose tet about 5500 cP 240 Phenolically modified pentaerythritol ester of rosin 1 20 Carbon black _ _ H0 The ink is prepared by (1) dissolving the phenolically modified pentaerythritol ester of rosin in the hydrogenated rosin methyl ester, (2) dispersing polystyrene in about two-thirds of the solution in a three-roll plant, (3) dispersion of carbon black in the remaining third of the resin solution in a three- rolling mill, and (4) mixing the two dispersions with a light mixing passage in a three-roll mill. The ink is used for printing in a type press "Little Joe". The printed matter is dried by placing it in a oven at 150 ° C for 90 seconds, in an oven at 200 ° C below 30 seconds and on a curved hotplate at 28800 for 3 seconds.

Example 25 A paste is prepared according to example ZH with closure of carbon black. The paste is used as an overpressure pee by printing in a sheet-fed lithographic press. The 10 20 25 30 35 . 10 ° C, number average molecular weight below 5000. 7904614-0 21 formed clear coating is dried in an oven at 150 ° C below 90 seconds.

Example 26 Finely divided poly (methyl methacrylate) with a particulate size of an average of 1 μm and with a molecular weight of approx 100,000 is obtained by expelling the heptane from a heptane dispersion, obtained by reverse emulsion polymerization sation. Poly (methyl methacrylate) and a pigment dispersing: i a mixture of resin and diluent using of a "Hoover Automatic Muller", and a uniform paste obtained. The final composition is: 'Weight parts 100 Ingredients Poly (methyl methacrylate) Hydrocarbon resin, mainly aromatic, based on polymers from petroleum and hard coal, softening point (ring and ball) 125 Varnish, phenolically modified penta- erythrytol ester of rosin dissolved in alkali-refined linseed oil with solubility parameter about 7.8, weight ratio ucnso, temperature below 0.1 s at 1so ° c. 75 Crude oil, derived from petroleum leum, solubility parameter approx. 7.8, ' volatility below 0.1% at 150 ° C. 25 Carbon black 25 Blue iron pigment 7 5 The ink is used for printing on paper in one lithographic offset printing and printing are of good quality tet. The printed sheets are guided at about 76 m / min during one 100 V / cm infrared ~ lamp with maximum power at about 1 μm (line heating model 5193-5 manufactured by Research Incorporated, Minneapolis, Minnesota, USA, powered by 230 V) at a distance of about 25 mm from the edge of the lamp reflector, which leads to rapid drying of the ink film. After drying, the printed matter is smear-free according to experiments performed with the Sutherland Ink Rub Tester (Sutherland Paper Co., Kalamazoo, Michigan, USA) weighing 1712 g during ten friction cycles. 790461440 10 15; 20 25 A.D Ingredients Example 27 An ink of the following composition is prepared the procedure set forth in Example 26.

Weight parts Poly (methyl methacrylate) 100 Hydrocarbon resin, mainly aromatic, based on petroleum monomers and hard coal, softening point (ring and ball) 10 ° C, number average molecular weight below 5000.

Varnish, phenolically modified penta- erythritol ester of rosin dissolved in alkali-refined linseed oil with soluble parameter of about 7.8, weight ratio holding 40:60, volatility below 0.1 at 1000 ° C. - vs Carbon black. _ * 25 Blue iron pigment _ 5 The ink is used for printing and dried as in 150 6G ~ Example 28 with the same result.

Example 28 An ink was prepared in the same manner as in Example 26 with, the following composition.

Ingredients Weight components Poly (methyl methacrylate), 100 Hydrocarbon resin, mainly aromatic, based on petroleum monomers and hard coal, softening point (ring and ball) 10 ° C number average molecular weight below 5000 260 Crude oil, derived from petroleum, solubility parameter about 7.8, volatility 9 below 0.1% at 150 ° C. 40 Carbon black 0 H0 The ink is used for printing and is thus dried * as in example 26. Thereafter, the ink is dry and smudge-free.

Example 29 An ink is produced in the same way as in the example 26 with the following composition. 10 15 20 25 30 35 cell pressure on cotton fabric and is brought to solidify through -at 1 ° C. 25 Ingredients Weight components Poly (methyl methacrylate) 100 Hydrocarbon resin, mainly aromatic, based on petroleum monomers and hard coal, softening point (ring and ball) 1o ° c, falling average molecular weight below suoo. 180 Crude oil, derived from petroleum, solubility parameter approx. 7.8, volatility below 0.1% at 150 DEG C. 20 Titanium dioxide _ »15 The paint is applied by stencil printing on glass and dried by heating in an oven at 135 ° C for 2 minutes.

The resulting film is dry and scratch resistant.

Exemgel 35 The ink of Example 26 is applied through the stone. infra- red radiation as in Example 27. The cotton cloth is washed in an automatic washing machine with detergent without loss of the picture.

Example 36 A paste of the following composition is prepared on the same as in Example 26.

Weight parts 120 Ingredients f Poly (methyl methacrylate) Hydrocarbon resin, mainly aromatic, based on petroleum monomers and hard coal, softening point (ring and ball) 1o ° c, ralmedeimolekylvikr under soon.

Varnish, phenolically modified pentaerythritol ~ ester of rosin dissolved in alkali refined linseed oil, solubility parameter about 7.8, weight ratio 40:60, volatility below 0.1% 160 100 -The paste is applied to the overpressure varnish in a litho- graphic offset pressure. The printed sheets are heated at 200 ° C for 2 minutes in a forced oven. Thereafter, the laying is dry and smudge-free.

Example 37 A paste of the following composition is prepared on the same as in Example 26. 7904614-o 7904611v0 10 15: _ the installation is dry and smudge-free. 20 25 30 35 Ingredients '10 ° C, number average molecular weight below 5000. 26 Weight parts Poly (methyl methacrylate) 100 Hydrocarbon resin, mainly aromatic, based on petroleum monomers and hard coal, softening point (ring and ball) 100 Varnish, phenolically modified pentaerythritol toluene of rosin dissolved in alkali refined linseed oil, solubility parameter about 7.8, weight ratio 40:60, volatility below 0.1% at 150 ° C; Crude oil, derived from petroleum, solubility parameter approx. 7.8, volatility below 0.1% at 150 DEG C. 20 Titanium dioxide lä The paste is applied to paper by roller coating and is heated by being conducted under an infrared lamp, which leads to rapid hardening of the pasta film. Thereafter, Example 38 A paste of the following composition is prepared on the same as in Example 26.

Ingredients 1 parts by weight Poly (methyl methacrylate) _ 100 K Hydrocarbon resin, mainly aliphatic, based on monomers from petroleum, softening point (ring and ball) 10 ° C, n number average molecular weight below 5000. '160 Carbon black '22 The pasta is applied to one treated with "Bonderit 100" cold rolled_ steel plate with knife. The coated plate is heated in a forced oven at 175 ° C for 5 minutes. After cooling the resulting coating is dry and rubbing resistant.

Example 39 The paste of Example 38 is applied to two pieces. of bleached poplin with squeegee. The coated fabrics are compressed 'with an iron at 12000 for 1 minute. After cooling a strong bond is obtained between the fabrics. §Example 40 The paste of Example 38 is pressed into a metal mold, 10 15 20 25 30 35 7904614-0 27 which had previously been coated with a mold release agent. The stuffed the mold is placed in an oven at 200 ° C for 10 minutes. After cooling, the casting is removed from the mold and is an exact copy of the form.

Example 41 An ink was prepared in the same manner as in Example 26 with the following composition.

Ingredients "Weight components Poly (methyl methacrylate) 100 Hydrocarbon resin, mainly aromatic, based on monomers from petroleum and rock carbon, softening point (ring and ball) 10 ° C, number average molecular weight below 5000. 160 Carbon black Å 26 Color-used for printing on paper in a litho graphic press and in a deduction press type Van der Cook. Print- the articles are dried by passing them under an infrared lamp, - as described in Example 26. Thereafter, the paint is dry and infection free. IN Example 42 An ink is produced in the same way as in the example 26 with the following composition. W Ingredients In Weight Parts Poly (methyl methacrylate) 100 Hydrogenated methyl ester of rosin with a viscosity of about 5500 cP 240 Phenolically modified pentaerythritol ester of, rosin - 20 Carbon black - 40 The ink is used for printing and dried as in Example 26. Thereafter, the paint is dry and smudge-free.

Example 43 - H8 Polymers and copolymers having the following compositions is prepared by emulsion polymerization. It is- held particle size is about 0.5 μm and the molecular weight about 500,000. 7904614-0 10 20 25 30 28 Approximate glass transition temperature -Example Comonomer card 7 trip, ° C 43 Methyl methacrylate s0 '% 105 f Styrene 40% H4 Methyl methacrylate 60% 105 Acrylonitrile 40% H5 Methyl methacrylate 80% 80 Methyl acrylate 1 20% - us 2 Methyl methacnylate us% 100 Acrylonitrile 20% Styrene 35% 07 'Akpylonirril 00% 93 g Styrene 40% us Acrylonifril '100% 105 _ These thermoplastic polymers are isolated as powders by evaporating the water from the emulsion. Inks each of these polymers is prepared in the same manner. as in Example 26 with the following composition.

Weight parts 100 Ingredients'-.

Finely divided thermoplastic polymer Hydrocarbon resin, mainly aromatic, based mainly on monomers from petroleum and coal, softening point (ring and sphere) 10 ° C, number average molecular weight below 5000. 0 Varnish, phenolically modified pentaerythritol toluene of colefonium dissolved in alkali refined linseed oil, solubility parameters of about 7.8, weight 40:60, volatility below 0.1% at 150 150 c., 75 Carbon black> 25 Blue iron fi igment 5 Each ink is used for printing and dried as in Example 26. Thereafter, each ink is dry and infection free.

Claims (10)

10 15 20 25 30 35 7904614-0 29 PATENT REQUIREMENTS i A paste-shaped composition containing discrete solid particles of a glassy thermoplastic polymeric material, which is made up of at least 51% of at least one monomer, which is an acrylate-type monomer or an aromatic monovinylidene monomer having a glass transition temperature of at least 50 ° C and a particle diameter between 0,05 and 50 μm, characterized in that the discrete solid particles of polymeric material are dispersed in an adhesion-promoting, cohesion-increasing organic material, the softening point of which is at or below room temperature, wherein the polymeric material and the cohesion-increasing material are present in a ratio in the range from 1: 6 to 1: 1 between the former and the latter. 2. A composition according to claim 1, characterized in that the glassy thermoplastic polymeric material is polystyrene or polymethyl methacrylate. 3. A composition according to claim 1, characterized in that the adhesion promoting, cohesion enhancing material is one of at least one resin and at least one diluent oil as a softening point reducing agent comprising mixture, the ratio of the resin to the oil being in the range of 1 : 0 to 1:15. 4. A composition according to claim 3, characterized in that the diluent oil has a solubility parameter between 7.0 and 8.5. 5. A composition according to claim 1, characterized in that the adhesion promoting, cohesion enhancing material is a hydrocarbon resin or a rosin ester or a mixture thereof. Composition according to Claim 5, characterized in that the rosin ester is a methyl ester of rosin, hydrogenated methyl ester of rosin, methyl ester of disproportionated rosin and / or an ester or modified ester of rosin with a polyhydric alcohol. v9o4s1u-o'i w 10 15 20 25 7. A composition according to claim 1, characterized in that it contains a coloring material. ° 8. A composition according to claim 1, characterized in that it also contains at least one curing agent in the form of a drying oil or an unsaturated alkyd resin. 9. A composition according to claim 8, characterized in that the curing agent is linseed oil, boiled linseed oil and / or isophthalic acid alkyd resin with a high oil ratio. 10. printing a pasty composition, characterized Method according to which on a substrate surface thereof, the composition contains (1) a coloring material, (2) discrete, solid particles of a glassy, thermoplastic polymeric material, which is made of at least 51,% of at least one monomer, which is an acrylate-type monomer or an aromatic monovinylidene monomer, and has a glass transition temperature of at least 50 ° C and a particle diameter between 0.05 and 50 μm and (3) an adhesion-promoting, cohesion-increasing organic material, the softening point of which is at or below room temperature, the polymeric material and the cohesion-increasing material being in a ratio in the range from 1: 6 to 1: 1 between the former and the latter, and heating the pressure surface of the substrate during such time and at that the composition melts. v9o4s14 ~ ól SUMMARY - ~~~~ -f ~ »w» It has been found that pastes of particulate polymers dispersed in a soft resin phase can be prepared which can be cured by fusing the thermoplastic binder. Polymers of the polystyrene and polyacrylate type are especially useful. Pigmented or oil-colored, these preparations have use as printing inks, uncoloured, they can be used as clear overprint coatings.