DE2721292A1 - Coating substrate with structured thermosetting resin - applied over active primer layer provided with barrier-forming material sections - Google Patents

Abstract

Thermosetting resin coatings having a structured surface, esp. of transparent or translucent unsaturated polyester resin, e.g. for wall and ceiling decoration, car interiors, aeroplanes, furniture and doors, are produced, pref. continuously, by (i) coating a carrier substrate with an active primer layer contg. radical polymerisation initiators, esp. peroxides, sensitisers, e.g. photo-sensitisers, activators, promoters and/or crosslinking agents for hardening the resin coating; (ii) providing the active primer layer, in sections, with barrier-forming substances which prevent upward diffusion or migration of initiator, sensitiser, etc. below sections, and (iii) finally applying the resin coating. The barrier-forming substances may be: (a) binders of cellulose derivs., hydroxyethyl cellulose, cellulose acetate, cellulose acetate-butyrate and/or nitrocellulose, polymethyl methacrylate and colophony esters, esp. contg. reactive double bonds, vinyl chloride-acrylate copolymers contg. active OH gps., allyl-modified polymeric plasticisers, polyurethanes and polyacrylonitrile, and (b) pigment compsns. carried by modified colophony esters.

Description

Process for the production of a thermosetting synthetic resin coating with

structured surface.

The invention relates to a method for producing a thermoset Synthetic resin coating with a structured surface, especially transparent or translucent unsaturated polyester resin, which has the textured surface is made by chemical means, that one by one under the coating The applied layer produces sections in the coating that have a lower Cure speed as the remainder of the overcoat, causing shrinkage @@ end of curing takes place, and the curing takes place at a slower rate Sections are pulled towards the shrunk part at the points so that the thickness of the coating is considerably reduced with the formation of depressions will.

Such a method is known from DT-OS 1 942 780. Here different images are formed with a printing ink on a carrier layer, which contains a hardening retarder for the synthetic resin coating to be applied over it the synthetic resin coating is applied.

Due to the presence of this retarder, the hardening of the portion will occur the coating over the one with the printing ink mixed with the retarder, coated part is delayed while the other part is hardened smooth, so that a Shrinkage occurs during curing.

To apply the synthetic resin coating, bsw. Solutions of unsaturated Polyester resins in monomeric vinyl compounds immediately before processing added a catalyst such as a peroxide and an accelerator and the like The reactive solutions obtained are then applied to the printing ink.

This process has the disadvantage that the polymerization with Catalyst and accelerator mixed solution starts very quickly, and the solution becomes unusable within a short period of time if it is not processed by then is. For this reason, the process is only used discontinuously.

The invention is based on the object of a method for production of a thermosetting synthetic resin cover with a structured surface in such a way that that eliminates the risk of premature gelatinization of the resin solution and their processing can be done on the side at the discretion of the processing can.

This task is thereby achieved in a method described at the beginning solved that a free radical polymerization initiators on a support, Sensitizers, accelerators, activators, promoters and / or crosslinking agents applies the active base layer containing the synthetic resin coating to cure, the active base layer is provided in sections with barrier-forming substances, the diffusion or migration of what is located under these sections Prevent the proportion of initiator, sensitizer, etc. from going up, and finally applies the resin coating.

In the method according to the invention, the disadvantages of the known Method overcome by the fact that the active basic method known from DT-AS 1 017 060 Use is made.

After that, the individual reactants are in a multi-stage Layering process applied so that bs @ w. the reaction of the unsaturated Polyester resin and vinyl monomer with the polymerization initiators, sensitizers etc. can only begin in the applied surface layers.

The respective solutions for the active base layer and the synthetic resin coating are relatively durable. The rapid triggering of the reaction occurs only then one, if the initiator etc. from the Aktivgrund ht in the applied synthetic resin coating intruded. This has the great advantage that with the invention designed processes fully continuously, i.e. from roll to roll, with optimal Degree of cure, d.

H. can be used with the lowest residual monomer content.

UP resins and reactive acrylic acid esters with unsaturated monomers are polymerized or hardened by a chemical reaction caused by free Radiakel is triggered. Free radicals are known to be caused by the decomposition of Peroxides, whereby the decomposition is activated by the action of accelerators, azo compounds, C-C compounds as well as the decomposition of certain ketones under the influence formed by ultraviolet rays will.

It is well known that the processing of highly reactive thermosets occurs because of the large number of reactive groups per mass, there is often a very strong shrinkage or Volume shrinkage. The volume contraction is almost absent in terms of time its entire extent to the onset of gelation and the finite solid state of the resin.

This mostly undesirable side effect of volume shrinkage is used at the present continuous catch for the manufacture of thermoset Synthetic resin coatings are used to create a structured surface to lend. The adaptation of the active basic method according to the invention for r die through riolumeal shrinkage or contraction of the resin caused by gelatinization and hardening Structuring the resin surface is the main subject of the invention.

It is well known that the volume shrinkage occurs in highly reactive resins around 8% and around for resins with a low content of reactive double bonds 54, which in their time course with the help of a [mercury dilatometer or an iomparatnrs according to Abbé can be measured.

With the new Durnplasten on dose acrylic ester, the shrinkage is round 5.4, because only the end groups can be networked.

There is thus the possibility of the extent of the volume contraction and consequently to design the structuring in the resin surface as desired, if you have suitable unsaturated monomers of different reactivity with one another combined.

It is known that when using highly reactive unsaturated synthetic resins to maintain a disruption-free production of the synthetic resin mixture inhibitors or delay added to the required processing time or pot life of the mixtures to extend.

The invention provides a process for continuous production of fast and trouble-free hardened thermosetting plastics with shrinkage contraction Structuring in the resin surface as desired by applying a Active base without the use of inhibitors or retarders.

By the colored printing of the active base with according to the invention compound, i.e. containing the barrier-forming substances, pinmented When printing, a structure appears in the transparent resin coating, exactly coinciding with the cough printed on the active ground, an embossed printing effect same.

Such color-structured resin coatings are used for application various substrates, experience elements tested for wall and ceiling cladding, Interior fittings for automobiles, airplanes and campers, for manufacturing of furniture, doors and the like.

In addition, the coatings produced according to the invention can also on laminated or non-laminated metal foil substrates, in particular from Aluminum. These can bsw. on plywood or Sn boards applied and then as reflective and insulating panels for ceiling and Wall cladding of apartments, fluorescent vehicles, camping cars, etc. can be used.

As is known, special peroxides were used for the active basic process developed with the property of rapid solubility in esters.

The method according to the invention is characterized in particular by this from applying an active base layer provided with a peroxide component.

The result that can be achieved according to the invention is surprising in that when it could not be foreseen that substances, printed on the active base, would be able to prevent the peroxide, which dissolves rapidly in esters, from immediately into those portions of the applied transparent synthetic resin coating which are in contact with the substances mentioned. They are substances known that when applied to plasticized PVC films, they prevent the plasticizer from to migrate into other surfaces or surrounding media. As such, e.g. Polymethyl methacrylate as a barrier plastic substance in US Patent 3,416,948 described. Barrier plastics have also become topical in recent years, which have a low permeability for gases, with the copolymer polyacrylonitrile at the top.

For the present application, however, such substances are not described in any way in the prior art.

Although a justification for the result that can be achieved according to the invention has not yet been established, but it can be said with certainty that the peroxide is below the printed pattern sections are present on the active ground, due to the barrier-forming ones Substances is prevented from doing so at the same speed in penetrate the overlying synthetic resin coating sections as the peroxide does the other active base cutouts, which are not covered by the printing varnish substances. In the latter, the transparent synthetic resin sections are covered by the peroxide an immediately onset of gel formation and hardening of the unsaturated synthetic resin triggered, coupled with a simultaneous decrease in volume, which is caused by its contraction forces thin out the not yet gelling and hardening synthetic resin coating sections Embossed colored structures that lie deeper in the level and are marked with are identical to the pattern printed on the active base, so that an embossed printing effect arises.

The following are preferred as barrier-forming substances Compounds used: binders based on cellulose derivatives, hydroxyethyl cellulose, Cellulose acetate, cellulose acetobutyrate, nitrocellulose or combinations thereof, Polymethyl methacrylate and rosins, such as methyl esters of rosin, modified Pentaesters and pentaerythritol esters, hydrogenated methyl esters, maleic acid-modified ones Esters and glycerol esters and pentaerythritol esters of polymerized rosin, Vinyl chloride-acrylate copolymers with active hydroxyl groups, allyl-modified polymeric plasticizers with a hydroxyl number of 40 to 50, polyurethane and polyacrylonitrile.

@ei Lere barrier-forming substances are pigment preparations, their Carrier material made from a modified rosin ester with a small number more reactive groups of the rosin.

Since the radical initiators from the active reason from below above @ take effect, the formation starts immediately in sections, Hardening and contraction in the same direction.

Alternatively or in addition to the content of free radical initiators The active base layer can also contain a photosensitizer that is under the influence by UV rays breaks down into radicals. As barrier-forming substances or in addition pigments are used for these, so that high-energy UV rays are applied to them be prevented the photosensitizers that are applied under the Pigments lie to break down into radicals at the same rate, like the uncovered photosensitizers. Preferably, in addition to a An active base layer containing a photosensilizer contains an activator Synthetic resin coating applied.

However, LS can also have an active base layer containing an actuator and a synthetic resin coating containing a photosensitizer is applied, then parts of the activator are covered. Finally, active base coats can also be used can be provided that have both a photosensitizer and an activator exhibit.

According to a preferred embodiment of the method according to the invention the hardening of the synthetic resin coating is thereby supplemented, coated and qualitative it is improved that the synthetic resin coating, which is already structured, is improved with the help of a photopolymerization hardens optimally and thus a surface with the lowest residual monomer content is obtained.

Adapting the active basic process according to the invention for production a thermosetting synthetic resin coating with a structured surface still offers an additional possibility, which consists in moving the vnn from the bottom to the top directed hardening effect by initiators etc. with an additional, however from top to bottom acting hardening process completes what in an optimal Through hardening of the outermost parts of the already structured coating results Application of known lacquer solutions in a thin layer by means of nozzles or printing This thin layer acts as it were on the structured coating surface an active top layer, as it contains suitable additives that match those underneath Layers can cure optimally, i.e. with the lowest residual monomer content In addition, this applied thin layer improves the filmed and cross-linked state the stacking and blocking resistance of the end product.

In addition, the active top layer can be treated with a final UV irradiation and the outermost adjacent UP resin layer by adding a UV sensitizer be optimally cured with the help of photopolymerization.

UV sensitizers exist, for example. from benzoin derivatives and combinations of benzophenone and other aromatic ketones with catalysts, e.g. amines.

The method according to the invention will now be based on drawings and the description of which is clarified, FIG. 1 being a schematic representation a machine process option for the continuous production of a thermosetting synthetic resin coating according to the invention with a structured surface, applied to a substrate such as paper, laminated or unlaminated aluminum foils or thin aluminum strips, shown from roll to roll; Fig. 2 is an enlarged Cross-section through the finished product shows, with the various layers for demonstration purposes are not shown true to size.

As can be seen from Fig. 1, a substrate 1 is back with the help from a doctor blade, Halzen nder cylinder screen application device 2 coated.

The back coat is dried by a heater 3, and by means of the second application device 4, the substrate is on the right side with a Picmentiertcn Orundieruan coated and dried by the drying device 5 D @@@ works 6 and 8, the first part of a pattern is printed on the primer and then briefly dried through 7 and 9.

The active base is then applied with the help of a hook, roller or cylinder screen application unit 10 applied and dried in the drying device 11. Then the transparent active primer with the substances that form the liarrery that make up the printing varnish as a binder contains' printed in the printing device 12 with the remainder Part of the desired pattern that will later be used as a structured This print varnish is briefly dried in the device 13 and then with the unsaturated resin mixture through the applicator 14 coated.

In the vertical heater 15, this unsaturated resin becomes after a short flash off it nelates and polymerizes, creating an immediately onset Shrinking effect that causes the colored structuring.

After cooling on a telephoned cooling roller 16 is the active cover layer is printed or sprayed on in a thin layer by the device 17 (not shown), whereby after evaporation of the small amounts of solvent in the area 18 the active cover layer itself in the area 19 for the most part cross-linked becomes and its additives at the same time optimal hardening of the extreme, already structured UP resin boundary layer, resulting in a blockable and stackable Coating, the surfaces of which are cooled by the chill rolls 20 before the material is rolled up in the winding device 21.

If UV initiators have been added to the active top layer and the recipe has been compiled accordingly, one of the Speed corresponding number of UV medium or high pressure lamps incorporated will.

Figure 2 shows, in a manner not to scale, a cross section produced by a method according to the invention shown in FIG. 1 Product, wherein the substrate 1 is provided with a rear-side ink coating 2 and With a primer 4 layered Sst. The first parts of a multi-colored print design 6 and ä are in one thene, covered by the transparent active base 10 last part. of the multicolored design 12 is located under the structured, transparent thermosetting synthetic resin cover 1'4 through the inner layer 17 is covered.

The back coating applied with the device 2 can Serve as a back adhesive layer when the finished product is used for surface finishing of wood-based materials are used and the adhesive layer is put together accordingly An adhesive layer on the back serving the same purpose, but for with Amino resins resinated carrier sheets and accordingly in their formulation composed of an amine plastic resin, is described in DT - PS 2 234 020.

In the process according to the invention, the adhesive layer on the back can be used can be put together from a binder mixture consisting of approx.

60 parts by weight of a vinyl chloride-acrylate copolymer with a OH content of 2, 20 parts by weight of a reactive polyester plasticizer with a nH number of around 40 and 20 parts by weight of a polyfunctional isocyanate Binding agents can be in solvent mixtures, consisting of ketones, different Esters and their mixtures with aromatics, with a solids content of 30 up to 50 percent by weight, most common ones can be used for pigmentation Pigments and extender pigments can be used.

To increase the solids content, organosols consisting of part of the above Adhesive layer and a remaining part of a pasteable PVC homopolymer with a mixture of a monomeric plasticizer and a reactive plasticizer can be used as a fast-setting back coating.

For the gelation of the rel. low application quantities of 25 to 409 / m2 those identified in Fig. 1 with 3, 5, 7, 9, 11, 13, 15 as well as 18 and 19 are sufficient Heating devices The crosslinking of the layer also takes place for the most part during the Fertitistellunn.

The Orundieruatt applied by the Vorrichtuan 4, must be a good one Have adhesion to the substrate and the overall coating sufficient stability to lend.

A coating with a binder mixture consisting of nitrocellulose, Alkyl resin (non-drying) and a polyfunctional aliphatic isocyanate showed excellent adhesion to paper and aluminum substrates it shows good compatibility with the following printing varnishes to be applied and the Aktivgrund. This layer, too, dries quickly and is networked to the greatest extent Part during the subsequent operations. However, the skilled person will also arise many other ways of putting together functional primers should be between 5 and 10g / m² dry.

According to the invention are pigmented on the transparent or translucent Active base print design parts applied with print varnishes, their solid substances are able to form a barrier for the active and peroxiri, which is located under the printed swatches and this prevents peroxide from to diffuse immediately into the sections of the unsaturated synthetic resin coating, those with the printed pattern sections on the active ground in direct relation stand.

The best result according to the invention is achieved with binders based on cellulose derivatives such as hydroxyethyl cellulose, cellulose acetate, Cellulose acetobutyrate, nitrocellulose and their combinations, polymethyl methacrylate and rosin esters, preferably with double bonds of the rosin that are still reactive, Vinyl chloride-acrylate copolymers with active hydroxyl groups, allyl-modified polymeric plasticizers with a hydroxyl number of 4n to 50 polyurethanes and polyacrylonitrile.

The following are known as rosin esters: methyl esters of rosin, modified Pentaesters and penteerithritol esters, hydrogenated methyl esters, maleic acid-modified ones Esters and glycerol esters and pentaerythritol esters of polymerized rosin.

Surprisingly, a group of pigment preparations showed up in particular well suited for pigmenting the printing varnishes used according to the invention The encapsulating carrier material of this range of pigment preparations consists of one modified rosin ester with a small number of reactive groups of the rosin.

With the above-mentioned binders of the printing varnish is the carrier material compatible and the assortment of this pigment group enables every desired one Hue; the pigment preparations can easily be put into the @. @. Incorporate binding agent.

The peroxide from the active base diffuses immediately into the solvent-based ones Printing varnishes and forms with the binders that contain reactive double bonds, networked, barrier-forming, patterned sections that make up the remaining portion of the peroxide under these printed swatches from to diffuse immediately into the sections of the unsaturated synthetic resin coating that are in direct contact with the print pattern.

Since it hardly seems possible, the required amount of effective Substances in the active primer, barrier-forming print varnish and in the curable UP synthetic resin coating To calculate optimally stoichiometrically in advance, this is experimentally done through preliminary tests to investigate.

For active base solutions that generally use nitrocellulose as a binder and therefore contain compatible resins and plasticizers, are free radical donors in Farm of organic peroxides are used, which have a fast Liislirinei t in e.g. The following are known as esters: cyclohexanone peroxide and mixtures of cyclohexanone peroxide with methyl ethyl ketone peroxide and methyl isobutyl ketone peroxide.

A flame retardant that has been brought onto the market in recent years Ketone peroxide, the acetylacetone peroxide with an active oxygen content of approx. 4,6, showed surprisingly good results in the examples given below, although it has not yet been mentioned for active base solutions. The peroxide content in such active base solutions is generally 10-20.

UP resins are mixed condensates of saturated and unsaturated dicarboxylic acids, e.g. maleic acid and phthalic acid with dihydric alcohols, e.g. 1,2-propylene glycol, which is a polymerizable vinyl compound, usually styrene, be solved.

Due to the wide variety of resin settings available on the market and types, the experiments were carried out with. an all-round resin in terms of its properties carried out based on isophthalic acid, with a shrinkage of 7 - ß. The UP resins based on isophthalic acid, shows high resistance to water, good chemical resistance and heat resistance. A finest adjustment was made by adding an allyl-modified Polyester with an acid number of 5 and a hydroxyl number of 40 and of one highly reactive diacrylic acid ester of bisphenol A with an acid number of u, 1 and a hydroxyl number of 16, mainly in order to be able to reduce the shrinkage -% - age to vary.

At the same time, the paintability with the above-mentioned networkable Thin-film coatings improved by these modifications, what their surface quality with regard to their scratch, staple and block feet, very close to the which brings decorative laminates based on melamine.

The UP resin mixtures were mixed with cobalt accelerators and styrene, and by adding ParaFfin in reactive solvents, the course of the Resin mixture promoted as well as the non-stickiness of the surface thereby achieved that the paraffin is known to have a very thin, airtight seal on the resin surface Layer forms so that inhibition by atmospheric oxygen does not occur The active solvents of the paraffin polymerize with and become Fully integrated in the polyester resin. Fumed silica was used as a matting agent used.

The composition of the active top-coat paints offers many possible variations, especially if you use a binder such as vinyl chloride-acrylate copolymer, reactive due to its free OH groups and compatible with many paint raw materials, goes out, so that it is possible to produce solvent-resistant paintwork. the dry quickly and can be crosslinked with isocyanates, melamine, urea and phenolic resins These are sprayed on in a thin layer, i.e. with a solid weight of 5 - 10 g / m² or rolled-on active top coats are already after the slight evaporation Solvent quantities block-proof and network themselves after a short time continue in the role.

In addition, additives can be added in small amounts, which per se in vinyl chloride-acrylic-urethanes as a light stabilizer and in the processing of Two-component polyurethanes as crosslinking accelerators with a specific anti-stick effect usually used, in a surprising way, the underlying, structured Cure UP resin layer with the lowest residual monomer content and thus the stability the structured pattern created by the completed Schrurnaf.

En is also part of the state of the art, since one is able to do so during hardening UP resins by means of high-energy radiation by adding a photosensitizer photopolymerization is supported to the extent that one hates peroxides and / or isocyanates in addition, so that the hardening accelerates and the adhesion on adjacent Layer th is increased. There is thus a cost-saving option, if mnn the isocyanate-containing active cover layer applied in a thin layer adding a photosensitizer; the photosensitizers used with good Resistance to light are of the benzoin ether and benzil dimethyl ketal type, the latter being the last Time gained importance.

The invention will now be described in greater detail on the basis of exemplary embodiments explained.

On paper or aluminum substrate strips, cut from for Coating suitable paper or aluminum-laminated or -non-laminated The layers are successively formed using the so-called "Meyer rod" applied, optionally on a back coating and a printing of the first part of the design, the primer on the right side can be dispensed with. After each work step it must be dried briefly or, in the case of use, the previously mentioned plastisols or organosols are gelled at a temperature which depends on the PVC homo- or copolymers used and the solvating ones Properties of the mono- or polymer plasticizers used.

The Meyer rod is a rigid rod with a thin metal wire around it certain thickness is wound and soldered at its ends to the rod. The rod is placed on the substrate strip, the on one level Unterlane is located, and a small puddle of the layering mass to be examined is stretched out in front of the stick. Then the stick is pinched over the substrate, leaving behind a layer thickness on the substrate that is the diameter of the wound around the Htab With rods wrapped with wires of different thicknesses Different layer thicknesses can be applied.

Conventional laboratory drying cabinets can be used for drying or gelling If you want to use organosols, plastisals or photopolymerizing agents Coatings using high energy radiation can be small ones available in the market Laboratory installations are needed, which preferably have a combined IR - UV - Use an oestration system, with the infrared part optionally regulated by means of an oheostat can be.

The sample strips are e.g. on a Teflon-coated transport tape guided at variable speed through the laboratory installation and the radiation sources exposed, as a result of which the (coating layers are completely polymerized or crosslinked will.

Example 1 A mass of the following composition was applied to the The reverse side of the present substrate is applied with a Meyer stick in one application amount from 20 - 25 g / m² dry matter.

Rear coating compound: Parts by weight: vinyl chloride / acrylate copolymer 85/15 (K value: approx. 40, OH content: 2%) Unsaturated, aliphatic, straight-chain Polyester with terminal OH groups 25 (hydroxyl value: 36-44, acid number: max. 3) Fungicidal, epoxidized plasticizer 5 (epoxy oxygen 5-6%) acrylamide resin (60 ß in xylene) 10 Parts by weight: aromatic diisocyanate, reaction product with a polyol (75%) 50 wax-like org. Amine accelerator with anti-sticking effect (10% in toluene) 10 color pigments and extender fillers 30 Rlltylacetat 25 methyl ethyl ketone 80 methyl isobutyl ketone 40 toluene 50 total weight: 400 solids content: approx. 45%.

This back coating has excellent adhesion on paper and aluminum substrates and makes this easier for the later processor Bonding to other substrates, e.g. wood-based panels, due to the content of Acrylate and acrylamide resin.

After this backing was dried, the top of the paper or Aluminum substrate coated with a primer, in an application amount of approx. 5 to 10 g / m2 dry substance.

The primer had the following composition: Primer: wt. - Parts: nitrocellulose 1/4 sec., Moistened with toluene 80 alkyd resin, non-drying, 60% in xylene 50 aliphatic. trifunctional isocyanate (75% solution) 50 Zn octoate (8% Zn.) 0.2 Maleinate resin solid parts by weight: (ring and ball melting range: 155-175 ° C 10 pigments and fillers 30 methyl ethyl ketone 75 methyl isobutyl ketone 65 Tolual 5 Cellos olve Acetat 15 Total weight: 400.2 Solids content: approx. Ao% The strips, coated with this primer and dried briefly, can be used with the first part of a two-tone print design, z.O. using the rotogravure printing process printed with conventional printing inks and then briefly dried. It then becomes the active reason for the event. printed primer applied in a weight ratio to the unsaturated resin coating of about 30:70.

The total weight of the reactive system, consisting of Aktivgrund and hardenable synthetic resin coating, is preferably 30 to 50g / m² solid substance, so that the solid substance ratios of the active base to the synthetic resin coating are preferred 10-20 g / m² to 23-46 g / m² should be.

The active basic solution had the following composition: active basic solution, transparent: parts by weight: nitrocellulose, moistened with butanol 85 (1/2 sec.) peanut oil modified. Alkyd resin (60 Ch in xylene) 60 maleinate resin, solid 20 dibutyl phthalate 9 Weight - Parts: ethyl acetate 100 butyl acetate 46 Tat tal butanol 15 total weight: 400 solids content: approx. 30 i: The following were added to this solution: acetylacetone peroxide (active oxygen: 4%) 40-50 after brief drying of this active base solution r-.iurdre the area with the part of the design that is in the gelled and polymerized transparent tiarzäberzug is responsible for the structured design part.

The barrier-forming Drucklacl have the following composition: Barrier-forming Printing varnish: (black) parts by weight: ethyl cellulose (low viscosity) 25 methyl ester of rosin 5 Sprit 200 Ethylglycol 50 Colophony-containing reactive pigment preparation 35 dissolved in toluene Total weight: 400 Viscosity: 18-20 "measured in a 4 mm Ford cup.

This last part of the design can be gravure, but preferably in the flexographic printing process, because with the help of the latter printing process the design parts cover the active base more evenly and thereby the structuring is formed in the resin coating with sharper contours.

After a short drying time, the unsaturated, pre-accelerated Synthetic resin coating in the @ .a. Applied in relation to the active base.

The composition of the coating composition was as follows: Unsaturated Resin solution: (transparent) Oew. - Parts: polyester resin, styrene-containing, highly reactive 3211 (based on isophthalic acid, acid number: 15) allyl mod. Polyester, hydroxyl number: 45 20 Monostyrene 10 Pyrogenic silica (matt finish) 27 Cobalt accelerator 1% in styrene 20 paraffin in reactive solvent 8 total weight: 400 It could immediately gelation and hardening of this unsaturated synthetic resin coating that begins at room temperature can be observed and, in the case of favorable m² contract ratios, from Aktivgrund to Synthetic resin coating, a simultaneous structure formation in the surface, which with the last printed part of the design, .O. in the form of a finest wood pore.

After hardening of the synthetic resin coating at room temperature or at elevated temperatures Temperatures from 80 ° to 100 ° C., The active top layer was applied with a simple spray gun The composition of such an active top layer was as follows: Active top layer: (transparent) parts by weight: vinyl chloride / acrylate copolymer, 2% OH groups 75 unsat. wheel chain. aliph. Polyester (see above) 25 Fungicidal, epoxidized polymer plasticizer 5 phosphite stabilizer 0.5 Ba-Cd stabilizer 1.2 UV light stabilizer (tetramethyl piperidine) 0.3 Waxy org. Amine accelerator, 10% 20 Parts by weight: Aliphatic aromatic Diisocyanate, 60% solution 50 Silicone-free leveling and @ et @ medium 3 butyl acetate 30 methyl ethyl ketone 60 methyl isobutyl ketone 50 cellosolve acetate 40 Toluene 30 Pyrogenic silica (matting agent) 10 Total weight: 400.00 Solid content: approx. 3 @.

The active top layer, which was sprayed on in a thin layer, dried very quickly and after 24 hours crosslinked to a block and stackable surface and polymerized by their accelerating amine additives activating those in contact, still generating monomers of the unsaturated hard synthetic material with a structured surface.

Example 2 This example was made in the same order as example 1. A gelling and hardening, well adhering organosal composition used.

Rear Organosol coating: Parts by weight: vinyl chloride / acrylate copolymer 85/15 35 (K value: 40, OH content: 2%) PVC homopolymer, paste quality, K value: 70 100 Unsaturated, aliph., Straight chain. Polyester with terminal OH groups, hydroxyl number: 36-44 30 fungicidal, epoxidized plasticizer 5 Parts by weight: straight chain Trimellitic acid ester 10 2,2,4-trimethyl-1,3-pentadiol diisobutylate 20 Ba-Cd stabilizer 3 org. Nitrogen derivative with an org. Metallver @.

(10% solution in ethyl acetate / ethylene chloride) 20 containing stearyl groups Polyurethane, 10% solution 20 methyl ethyl ketone 50 ethyl acetate 30 containing aromatic compounds Hydrocarbon thinner 52 diisocyanate, reaction product of polyols and a aromatic diisocyanate (75% solution) 25 total weight: 400 solids content: approx. 50@.

The mass was prepared in such a way that the vinyl chloride-acrylate copolymer dissolved in the listed volatile solvents, separately the pasteable one PVC homopolymer in the mono- and polymer plasticizers paste and paste both components intimately mixed with each other.

The result is an organosol that can be pileded in one desired shade.

Liquid pigments and exteoder pigments can be used for pigmentation however, silenic natural iron oxide pigments and chromates are avoided, which can disturb the thermal stability.

The isocyanate is used for the purpose of completing the Organosole added just before use.

A dry weight of 15-25g / m² is sufficient for the backside when dry, so that about 30-50g / m² of the organosol are applied to the back of the substrate got to. The coating dries at 60-80 ° C. fast and can at 140-160 ° C. in 45 up to 60 sec. be gelled. In the case of continuous production, this runs through Back coating applied in the first place the whole system and is thereby completely networked. The added stearyl-containing polyurethane gives the surface an excellent release effect, but the amounts given should not exceeded in order not to disturb the later gluing to other documents.

The following primer can be applied with the same primer as in Example 1 and turn over printed with a conventional printing varnish. Of the Aktivgrund can use the following combination.

Active base solution, transparent: Parts by weight: Nitrocellulose, moistened with butanol, 1/4 sec. 95 Ordinary oil mod. Alkyd resin (60% in xylene) 55 maleinate resin, solid 20 dibutyl phthalate 10 dioctyl phthalate 5 ethyl acetate 100 utyl acetate 40 toluene 70 butanol 5 total weight: 400 Solids content: approx. 32. í This solution was added: Cyclohexanone peroxide (Active basic quality) 80-100 (active oxygen content: approx. 11%) This iadical donor is not unsuitable for heat curing, so that the unsaturated synthetic resin coating gelled and hardened at room temperature. should be. In such cases you can the advantages of an active top layer sprayed on in a thin layer are used, in order to optimally reduce the residual monomer content with the help of UV rays and the to give the outermost UP resin layer a good stacking and lock resistance low surface temperatures.

The briefly dried active base layer was barrier-forming with the following Printing varnish printed: Barrier-forming printing varnish: (black) wt. - Parts: vinyl chloride-acrylate copolymer (K value: 40, OH content 2%) 50 allyl modified. Polymer plasticizer (acid number: 8, OH number: 40-50) 20 butadiene acrylonite (MÄK-soluble) 10 MÄK 60 butyl acetate 30 ethyl glycol 60 Tert. Butanol 10 pigment preparation containing rosin 100 toluene 60 gas weight: 400 viscosity: 18-20 "measured in a Ford cup 4.

After a short drying time, the UP resin mixture was mixed in the above ratio applied to the active base. The composition of the mixture was as follows: Unsaturated Resin mixture: Parts by weight: Modif. UP resin, containing styrene, highly active 300 (isophthalic acid base) Diacrylic acid ester of bisphenol A 20 Allyl modified polyester (hydroxyl number 40-50) 20 Fumed silica (matting agent) 20 Monostyrene 10 Cobalt accelerator 1% in styrene 15 paraffin in reactive solvents 10 dimethylethanolamine 5 Total weight 400 After applying these unsaturated resin mixtures the gelling of the coating started immediately and the structuring was evident almost simultaneously; at a moderately increased temperature, the hardening process can be accelerated, however, a temperature of 60 ° to 80 ° C.

Not to be exceeded. The remaining monomers in the outermost Coating layer can be applied by spraying in a thin layer (3 to 5g / m² dry) with the help the following active top layer, provided with a photosensitizing additive, are optimally polymerized and crosslinked.

Active top layer: Parts by weight: vinyl chloride / acrylate copolymer 85/15 75 Unsaturated, straight chain, aliphatic. Polymer soft 20 fungicidal, epoxidized Polymer plasticizer 5 Ba-Cd stabilizer 2 Organic phosphite 0.5 Waxy org. Amine accelerator 20 (10% solution in toluene) with anti-sticking effect Pyro @ ene Silicic acid (matting agent) 12 leveling and bedding agent (silicone-free) 2.5 methyl ethyl ketone 80 Toluene 20 Aromatic-rich hydrocarbon thinner 100 (evaporation number: 46) Di-ethoxyacetophenone 2 benzophenone 1 reaction product of an aliph. and aroma.

Diisocyanate in 60% butyl acetate solution 60 total weight: 400 Solids content: approx. 36% The viscosity is adjusted to atomization.

After the solvent has evaporated, the coated substrate is covered UV-energy-rich irradiation lamps completed in a last work step, provided with a block and stackable, structured surface.

L e r s e i t e

Claims (16)

PATENT CLAIMS 1. Method for producing a through-plastic Synthetic resin coating with a structured surface, especially transparent or translucent unsaturated polyester resin, which has the textured surface on chemical bending is produced by going through one under the cover applied layer creates cutouts in the coating, which with a smaller Cure faster than the remainder of the coating, causing shrinkage takes place during hardening and those hardening at a slower rate Sections in the direction of the shrunk part are related to the places so that the thickness of the coating / with the formation of depressions is considerably reduced is dg. that a free radical polymerization initiators, Sensitizers, accelerators, activators, promoters and / or diluents Applying the active base layer containing the synthetic resin coating for curing, the active base layer provides sections with barrier-forming substances, the diffusion or migration of what is under these sections Prevent the proportion of initiator, sensitizer, etc. from going up, and finally applies the resin coating. 2. The method according to claim, dg. That one works continuously. 3. The method according to claim 1 or 2, dg. That one with a peroxide content applied active base layer. 4. The method according to any one of the preceding claims, dg. That one applying a synthetic resin coating containing an accelerator. 5. The method according to any one of the preceding claims, dg. That as bar- Barrier-forming substances used the following compounds are: binders based on cellulose derivatives, hydroxyethyl cellulose, Cellulose acetate, cellulose teobutyrate, nitrocellulose or combinations thereof, polymethyl methacrylate and rosin esters, preferably with double bonds of the rosin that are still reactive, such as methyl esters of rosin, modified pentaesters and pentaerithritol esters, hydrogenated methyl esters, maleic acid modified esters and glycerol esters and pentaerythritol esters of polymerized rosin, vinyl chloride-acrylate copolymers with active Hydroxyl groups, allyl modified polymeric plasticizers with a hydroxyl number from 40 to 50, polyurethane and polyacrylonitrile. 6. The method according to any one of claims 1-4, dg. That as a barrier-forming Substances pigment preparations are used, whose carrier material consists of a modified Rosin ester with a small number of reactive groups of the rosin consists. 7. The method according to any one of the preceding claims, dg. That one an active base layer containing a photosensitizer is applied, which under Influence of UV rays breaks down into radicals. 8. The method according to any one of the preceding claims, dg. That one an active base layer containing a photosensitizer and an activator containing synthetic resin coating applies. 9. The method according to any one of claims 1 - 6, dg. That one is a Active base layer containing activator and one containing a photosensitizer Resin coating applies. 10. The method according to any one of the preceding claims, dg. That one an active base layer containing a photosensitizer and an activator brings up. 11. The method according to any one of the preceding claims, dg. That one before applying the active base layer, optionally the carrier substrate first with an @ primer and a print design or part of it. 12. The method according to any one of the preceding claims, dg. That one the backing base is sealed with a backing coating compound or film. 13. The method according to any one of the preceding claims, dg. That one the barrier-forming substances in the form of an independent, single-color print pattern or in the form of part of a multicolored print pattern. 14. The method according to any one of the preceding claims, dg. That one the hardening of the synthetic resin coating thereby supplements, accelerates and qualitatively improves the fact that the synthetic resin coating, which is already structured, is improved cures optimally with the help of a photopolymerization and thus a surface with the lowest residual monomer content. 15. The method according to any one of the preceding claims, dg. That one The structured synthetic resin coating is sprayed on in a thin layer and rolled on or printed active top layer covers, so that this self through its additives networked to a block and stack solid surface and in a top to bottom The hardening caused by the active base layer is initiated towards the bottom through an accelerating additive effect or alternatively through an accompanying one Photopolymerization, supported. 16. The method according to claim 15, dg., An active top layer is applied, the additives of which consist of a photosensitizer combined with an activator.