DE1669771B2 - METHOD FOR MANUFACTURING A FOAM PRODUCT WITH A STRUCTURED SURFACE - Google Patents

Description

DT-AS15 04 106 have been used. For example, for influencing the viscosity and the Viskosi, a first layer of a resin mixture with stability of the coating mixtures and a blowing agent is applied to the surface of a basic foam properties of the foamable layer, which is important with the help of any facility. Suitable plasticizers, such as with a backward-running cover, are also described in DT-AS 15 04106,
roller, a scraper blade or a similar loading As in accordance with DT-AS 15 04 106, the coating

Layering device, can be done. According to the invention, the mixture also contains a metal stabilizer added to the decomposition catalyst. The coated base is then heated to decrease flows of light and heat,
around the thermoplastic resin layer at least io The mixtures can, depending on the desiredi, partially gel and convert them into a solid mass containing pigments corresponding to the color, practically converting. The gelled coating is then transferred to a cover device in which organic or inorganic dyes, ink or the like, can be used to create a pattern on the surface of the manure. Usually about 0.5 bi-lined web is printed on. The printing inks to 15 about 5 parts of dyes applied to 100 parts of resin composition contains a chelating agent for the foamable mixtures contain there

the metal catalyst. Then apply a second addition to an effective amount of a blowing agent. Jf Layer the resin mixture on the printed surface to increase the amount of blowing agent used applied, whereupon the composite structure is by a practical limit, the greater is the Heating device is passed through, in which ao expansion of the foam.

rather the temperature of the blowing agents that are on the base web

Composition is increased so far that it is effective to the extent that it is below de. ' blowing agents in the first layer with exposure to the decomposition temperature of the resin used the places at which the chelating low temperature can decompose; those in the Agent was applied, is decomposed and both 25 DT-AS 15 04 106 described blowing agents are also Coatings which are completely solvated can be used according to the invention. Most preferred and fused together. Then those blowing agents, which are above the the product will decompose through a cooling chamber - elastomer point of the resin mixture. Guided here. The one with the printed pattern in through is at least partial gelation of the which is the chelating agent, in 30 foamable mixture allows so that on Foam that is in contact has only part of its surface - a pattern can be printed on it, wise or practically no foam structure. If after the foamable coating has been applied

The product is intended to be used in places where it may be heated to the coating as mentioned is not subjected to any particular wear and tear, it can be used to turn the mixture into the gel state Coating can be omitted entirely. When 35 lead. Beauf in the description and in the claims When a pattern is printed on the first layer, the term "gel" applies to both the partial the second layer of the resin mixture should be carried out (at least up to the elastomer point) be careful; otherwise it can also be opaque as well as complete solvation of the resin be. The base coat can be used as part of the product or resins with the plasticizer. The heating remain or can be limited, for example, by reducing the duration and temperature, pull to be separated from the finished product. The decomposition of what is in the mixture in DT-AS 15 04 106 described base layers of blowing agent to prevent. When using the besind also suitable according to the invention. preferred polyvinyl chloride mixture, the temperature

If a felt web is used as the base layer, the temperature of the mixture is preferably about 116 to this can be increased with waterproof and strength- 45 135 ° C. In general, the furnace temperature should match Synthetic resins are impregnated. door are slightly higher so that the coating

The resin mixtures and the application of the same are able to achieve the desired temperature. Presence Also described in more detail in DT-AS 15 04 106, a fusion of the resin is carried out ben. The most preferred and most widely used- complete solvation with the plasticizer related Resin blends are the vinyl polymers, 50 as this prevents the adhesion of the later applied like vinyl chloride. Coating improved.

The resin blend usually also includes Table I which shows the preferred temperatures and

a plasticizer, which is used to determine the time ratios when using the preferred Strength and flexibility of the mixture and synthetic resin:

Table I.

Film condition ·) Temperature of the oven temperature ( ⁰ C) exposure time

Resin with air circulation (in s)

Elastomer point 116 to 149 121 to 204 10 to 300

Amalgamation 171 to 190 177 to 232 60 to 240

Foamed 171 to 204 177 to 232 60 to 240

*) 0.35 mm plastisol on 6.35 mm thick cellulose felt base layer, with 9% vinyl acetate and 30% petroleum hydrocarbon on a wire mesh.

The printing composition contains dye and solvent carriers, and at least one printing medium suitable chelating agent are those containing a chelating agent for the metal bonds which are used at temperatures below the catalyser of the blowing agent. The printing agents contain the settling temperature of the catalyzed blowing agent in usually a carrier for the dye, such as the foamable mixture soluble or otherwise vinyl resin, and a plasticizer for the resin in order to be diffusible and which metals to molecularly adhere well to the surface to be printed Ability to bind. To count on this. The chelating agent used is a substance containing 8-hydroxyquinoline, 2-M2rcaptobenzothiazole, Ali, which has a complete or at least partial zarin, purpurine, picolinic acid, quinolinic acid and its wise formation of a chelate complex with the partial methyl ester, ethylenedinitrilotetraaceionitrile, diguanine catalyst Area above or below the propyl gallate and other higher molecular gallus site to which it has been applied. acid esters, phthalonitrile, partial esters of ethylenedinitrilo-By changing the chelate concentration, tetraacetic acid, iminodiacetic acid, «,« '- dipyridyl, its application thickness or its penetration speed - poly - «- pyridyl, N, N-disalicylidene-1,2-propanediamine, speed in the gelled foamable coating and 15 ”-nitross-jS-naphthol, acetoacetanilide, o-acstoacet the extent of the suppression of the blowing agent cerisidide, salicylic acid, barbituric acid, acetyl avetone. Settlement to produce layers of foam, other chelating agents and some of the mitalle, of various heights can be controlled. This system, by which any means can sequester, can be used for the manufacture of sculptured products listed in Table II,
of the type described in US Pat. No. 2,961,332
be turned. According to this patent specification
this effect is achieved by using mixtures under Table II

different blowing agent contents placed side by side.

prints throw. The printing device ^{must therefore chelate metals}

can print relatively thick layers, 25

to produce a foam film of considerable thickness gluconic acid, 5-sulfosalicylic acid
to be able to. According to the invention, with the help of a tartaric acid
conventional coating device a by-citric acid
colored uniform foamable coating applied to disodium 1,2-dihydroxybenzene and the pattern by means of high-speed 3,5-disulfo a
keits printing presses that only apply a thin layer of 8-hydroxyquinoline-5-sulfonic acid
able to close, be imprinted. The selection of the chelating agent for the blowing agent - mercaptoic acid
Metal catalyst depends on a number of different- dithiotartaric acid
ner factors. The most critical factors are the 35 ethylenediamine (en)
respective blowing agents, the stabilizer and the plasticizer in the mixture as well as the fusing and N-methylethylenediamine
Decomposition temperature of the resin. The usefulness of propylenediamine-1,2
A certain chelating agent can be trimethylenediamine
can be determined by a simple experiment. The foam 40 2-hydroxy-1,3-diaminopropane
capable test mixture is applied to a base coat

applied and heated to gel the mixture, cis-1,2-diaminocyclohexane
but without decomposing the blowing agent. Subsequently, spaced apart trans-1,2-diaminocyclohexane
parallel lines of test inks of different compositions 45
concentrations, for example with 5, 10 and 20% of the histamine
chelating agent, on the surface of the ge 2-aminomethylpyridine,
lined coating applied. A wear layer is placed over the printed N-hydroxyethyl-2-amino surface, and ethylpyridine, pyridoxamine,
then the sample is heated to convert the mixture to 50 1,2,3-triaminopropane,
fuse and decompose the blowing agent. The diethylenetriamine
Effect of the chelating agent in question with N-2-hydroxyethyl-ethylenediamine
the mixture in question and among the 2,2-dimethyl-1,3-diaminopropane in question
Conditions can be easily identified by looking at a

See cross-section through the sample. As a general 55 N-aminoethyl-2- (2-amino-

As a rule, it can be said that preferably a sub-ethyl) pyridine, triethylene Co

differed from at least about 11 ⁰ C between the Tem- tetramin, Äthylen- <x, * '- (2-amino-

temperatures should exist at which the flatulent methyl) pyridine, /?, /? ', / 9 "-Triamino-

agent under the action of a catalyst and in which triethylamine, tetrakis- (2-araino-

the chelate catalyst / blowing agent combination cerium (ethyl) ethylenediamine

puts. When using a blowing agent that is 2-mercaptoethylamine
decomposes below the gel temperature of the mixture,

the inhibitor is preferably applied to the base layer methylthioethylamine,

applied and then the foamable 2-amino-2'-hydroxydiäthylsulfid

Mixture applied over the inhibitor. Optionally 65 bis (2-aminoethyl) sulfide

the inhibitor can also be applied to 1,2-di- (2-aminoäthylthio) -ethane before gel formation

Surface of the viscous coating applied glycine but this is a more difficult process.

Cu Cu Pb, Cu Co Cd, Zn, Pb, Ni, Zn, Ni, Cu, Cd, Zn, Pb, Cu, Mn, Co Zn, Pb Cu, Zn Cd, Zn, N ", Ag, Co Cu Ni, Cu Cd, Zn, Ni, Ag, Ni, Cu, Ag Zn, Ni, Cu, Cu, Co Cd, Zn, Ni, Cu, Co Cd, Zn, Ni, Co Co Cu, Zn, Ni, Cu, Cd, Zn, Ni, Co Ag, Ni, Co Zn, Ni, Cu, Cu, Co Cd, Zn, Ni,

CD, Zn, Pb, Ni, Co Cu Zn, Ni, Cu Ni, Cu, Co Zn, Pb, Ni, Cu, Co

Table II (continuation)

Chelating agent Metals Cd, Zn, Ni, Cu, Ν, Ν-dihydroxyethylglycine Cd, Zn, Ni, Cu, Co Co 2-AminoäthyIpyridin-N-mono- Cd, Zn, Ni, Cu, acetic acid Co «-Alanin Zn, Pb, Ni, Cu, Co Valine Cd, Zn, Cu, Co Norvalin Cd, Zn, Ni, Cu, Co Cd, Zn, Pb Leucine Zn, Cu, Co Zn, Ni, Cu, Co Norleucine, asparagine, proline, Cd, Zn, Ni, Cu, Cd, Zn, Ni, Cu, Tryptophan, methiomine Co «, / J-diaminopropionic acid, Zn, Ni, Co 1-ornithine, lysine, arginine, cysteine Histidine, N-acetamidoiminodi- Cd, Zn, Pb, Cu, acetic acid, N-methoxyethylimino- Co diacetic acid, N-hydroxyethylimino- diacetic acid, / 5-mercaptoethyl iminodiacetic acid, N-methylthio- ethyliminodiacetic acid, ethy! - diamine-N, N-diacetic acid, ethylene diamine tetraacetic acid, Aspartic acid, glutamic acid, Iminodiacetic acid, N-methyl- iminoacetic acid, N-cyanomethyl- iminodiacetic acid, ethylene-bis- N, N '- (2-aminomei' y -pyridine-
N, N'-diacetic acid Ä ylen- diam η Ν, Ν'-dipr pi isic acid, N-Hydroxyäthyläi yl n- diaminetriacetic acid Glutathione Iminodipropionic acid Nitrilotriacetic acid

Nitridotripropionic acid

1,2-diaminocyclohexane

N.N'-tetraacetic acid, ethylene

diamine-N.N'-dipropion-

Ν, Ν'-diacetic acid

Ethylenediamine-N, N'-tetra-

propionic acid, 2-aminoethyl

pyridine-N-monoacetic acid,

Diethylenetriamine pentaacetic acid

Mn, Co

Zn, Ni, Cu, Co

Cd, Zn, Pb, Cu,

Co

Cd, Zn, Ni, Cu, Co, Mn

The chelating agent should also have a chelation constant with the metal present in the metal catalyst of at least 1 · 10 *. The chelation constant is a measure of that Ability of the chelating agent to complex with the metal and is through the following equation determines:

Chelating agent (I) + metal (II) -> - metal helate (III), in which the chelate constant of the equation

(III) Chelate constant K = "^ T ^ T

enough

The concentration of each term in the equation can also be measured in moles per liter, where K must be at least 4.0. The most common metals used as catalysts for blowing agents • lead and zinc salts. 2-mercaptobenzothiazole and

? 8th

N.N'-disalicylidene-l ^ -propanediamine are with zinc and alizarin and nitroso - ^ - naphthol are with lead particularly effective.

The solubility of the chelating agent in the foamable mixture at the decomposition temperature represents a significant factor in the process. When using easily soluble chelating agents Means, decomposition of the blowing agent can be completely avoided. With less soluble

to chelating agents, the concentration of the agent in percent has a decisive influence on the control of the decomposition. The less soluble chelating agent may be of the dye type be in a finely ground state so that it is either easily soluble or diffusible at working temperature will. The diffusibility of the chelating agent in the foamable mixture can can be improved by using a porous mixture. This can be done, for example, by using

ao generation of a dry mixture of synthetic resin, plasticizer, Achieve blowing agents, etc. A relatively firm but porous layer can be achieved by heating this dry mixture to sinter the particles together. Another method

It consists in applying the chelating agent in liquid or dry powder form to a liquid foamable mixture which contains a solvent for the chelating agent.
The amount of material used in the printing ink determines to a large extent the degree of foam inhibition. Particularly good results have been obtained with an excess of chelating agent over the calculated required molar amounts. Some of these agents cause discoloration, which in most cases can be avoided by pigmentation if desired.

After printing, the second mixed layer can be applied. As mentioned, this can the second mixture can be the same or a different mixture than the first foamable mixture. Using different mixtures, which are not readily compatible with each other, can before Applying the second mixture, an adhesive layer can be applied. If a decoration pattern has been printed on the surface of the foamable mixture, the second mixture must be transparent or translucent so that the printed pattern is visible through the mass This second mixture mass serves primarily as a wear protection layer, which is why its thickness is only depends on the abrasion resistance of the final vinyl product it is asked for. In general, a layer thickness of about 0.05 to 0.30 mm is sufficient, to give the end product good abrasion resistance.

The product is heated to a temperature that allows the resin to melt through completely Solvation of the resin with the plasticizer uid to decompose the blowing agent without decomposition of the Blowing agent in the areas of catalyst C: elate formation sufficient The temperature of the whole mixture mass must be the melting temperature of the Reach resin so that a product of maximum strength is obtained. When using the bevonu? - ten vinyl resin will be a merger with one:

Temperature of about 149 to 190 ⁰ C achieved. In addition, the entire mass of the foamable mixture must be heated to a value at which the blowing agent decomposes

509584/469

preferred high-temperature blowing agent, foaming occurs only after the resin mixes have melted on.

The heating to effect fusion and foaming can be done in a forced air hot air oven or in another heating device. For example, the product can be exposed to radiant heat or, alternatively, dielectric heating can be used.

After exiting the oven, the foamed and fused product is cooled. That Cooling can be done by simply exposing the product to outside air. The speed of movement the base layer along the processing device as well as the distance of the fusion furnace from the end of this device can therefore be chosen so that the product is sufficient There is time to cool down. Optionally, the cooling can also be accelerated by applying cooling air to the Melted and foamed mass is blown, a fine water spray used or cooling rollers be used.

After cooling, the product is discharged from the processing device. It can now depending on the intended use in the form obtained by the manufacturing process used or cut into appropriate shapes. The products made according to the invention have because of the foam layer located on the surface or immediately next to it excellent elastic properties. They are also characterized by an accentuated three-dimensional structured appearance, the structure of which corresponds to the printed pattern. About that In addition, the products produced according to the invention have the foam mass because of the layer good thermal insulation properties and are therefore warmer in winter and cooler in summer than conventional ones Resin surface coatings.

As mentioned, the foamable mixture can first be calendered prior to decomposition of the blowing agent be brought into web or strip form, which is described in the US-PS 29 64 799 manner can be effected. According to this patent, a high-temperature blowing agent, such as azodifonnamide- (l, l'-azobisformamide), used. The resin mixture is used to combine the components of the mixture in a Banburry mixer or the like. mixed and then mixed to form a sheet, sheet or strip of the desired thickness guided by calender rolls The layer can have self-supporting rigidity and is then subjected to a printing process or the like in which the chelating agent is applied to one or both of the Areas is applied in the desired areas. The location is then heated to the blowing agent in the desired areas not in contact with the chelating agent to decompose and thereby produce a product that corresponds to the degree of decomposition of the blowing agent has a surface with changing levels. The layer can be before or after decomposition of the blowing agent can be provided with a base layer or with a wear-resistant layer.

The products according to the invention can be used for numerous Applications are used. They make excellent floor, wall and ceiling coverings and also make excellent

Upholstery fabrics, draperies and curtain materials, with which a wide range of effects can achieve. The skilled person are of course numerous other areas of application for products according to the invention common.

Example I.

A foamable plastisol was prepared by mixing the following ingredients in a conventional one ίο Cowles mixer made:

Parts
Vinyl chloride-vinyl acetate copolymer

(dispersible) 100

Dioctyl phthalate 60

Alkylaryl hydrocarbon 5

Dibasic lead phosphite 1

Finely divided titanium dioxide 2

Azodicarbonamide 2.5

ao The plastisol was applied as a uniform coating 0.25 mm thick on the surface of an approximately A 0.63 mm thick cellulose felt sheet is applied, containing 9% vinyl acetate and 30% hydrocarbon resin was coated. The felt sheet was previously with

»5 treated in an amount of about 113 g / m ^{1 of} a finish coating of the following composition:

Parts

Acrylic resin (soft) 50

Acrylic resin (hard) 50

Water 100

The plastisol coating was then heated to a temperature of about 135 ° C to form the coating to a movie with a; ' To gel elongation or extensibility of 200%. The gelled web was then passed through a rotogravure press in which three different ink compositions were printed on the web. One of these inks had the following composition: ♦ ° parts

Vinyl chloride-vinyl acetate copolymer ... 10.5

Pigments 13.7

Dioctyl phthalate 8.0

Methyl ethyl ketone 55.3

2-mercaptobenzothiazole 12.5

An organosol mass of the following composition was applied to the printed surface in a uniform layer about 0.1 mm thick:
Parts

Vinyl chloride polymer

(dispersible) 100

Dioctyl phthalate 17

Tricresol phosphate 8.5

Stabilizer 2.0

Mineral spirit 18

The web was then passed through an oven in which the coating was gradually heated ^{to a temperature of about 177 to 190 ° C.} The two coatings fused and the blowing agent decomposed, forming a product with a foam layer about 1.0 mm thick and a solid layer about 0.01 mm thick covering the foam slides. the ink composition containing 2-mercaptobenzothiazole. The depth of the

The dimple was about 0.63 mm. The product resulted in an excellent floor covering with high levels of abrasion and dirt resistance and excellent indentation recovery.

Example 2

On the surface of a peelable paper, a plastisol of the following composition was applied as a uniform Coating about 0.25 mm thick applied:

Parts
Vinyl chloride-vinyl acetate copolymer

(dispersible) 100

Dioctyl phthalate 55

Alkylaryl hydrocarbon 10

Zinc stearate 3

Finely divided titanium dioxide 5

Azodicarbonamide 2.4

The paper was provided with a coating of a complex compound of the Werner type, in which a trivalent chromium atom is coordinated with an acrylic carboxylic acid residue with at least 10 carbon atoms. Such a composition is described in US Pat. No. 2,273,040. The plastisol coating was then heated to about 149 ° C for 1 min to gel the mixture, whereupon the gelled coating has been cooled. The gelled product was then passed through a rotogravure press, which printed a five-color print pattern on the surface of the gelled coating. One of the printing materials used had the following composition:

Parts

Vinyl chloride-vinyl acetate copolymer ... 10.5

Pigments 13.7

Dioctyl phthalate 8.0

Methyl ethyl ketone 55.3

N.N'-disalicylidene-1-4 propanediamine 12.5

The organosol mixture according to Example 1 was then applied to the surface of the printed, coated Coating applied where it formed a uniform coating about 0.13 mm thick. Thereafter the coatings were heated to a temperature of about 171 to 185 ° C to form the mixtures together to fuse and completely decompose the blowing agent, leaving one with a wear layer of about 0.13 mm thickness of the same material

ίο bonded foam layer about 1.0 mm thick was formed. The fused and foamed product was then cooled and the peelable Paper peeled off the back of the product. The product obtained had a foam base layer with a wear-resistant layer of solid resin that is uniformly connected to it. That Product had in its surface at the points where the N, N'-disalicylidene-l, 2-propanediamine containing printing ink had been applied, pits about 0.5 mm deep.

Table III shows various other chelating agents and the metal catalysts that can be used on the im Example 1 were used with similar results.

Table III example Chelating Agents Metal Catalysts

3 alizarin Lead phosphite 4th 1,8-dihydroxy Lead phosphite anthroquinone 5 Acetoacetanilide Lead phosphite

Numerous changes and modifications are of course possible for the person skilled in the art without this the scope of the invention is left.

2

Claims (3)

1β 69 771 ι in sections a color with good heat absorption Claims: tion ability is applied. This method has the drawbacks that it is due to the use of L method for the production of a foam radiant heat is limited, only the production of a product with a structured surface by inserting a 5 of products with light-colored and convex blowing agent into a foamable molded raised surface parts and resin approach and subsequent heating of a merely the application of thin layers By comparing the resin batch to a specific foamable material, the temperature at which the blowing agent decomposes is allowed portions of the averaging method will be applied in the invention, layer by said one substance which prevents it exploits a chemical principle, the rate of decomposition of the blowing agent, the invention provides a process to the relevant sections either increases the H Creation of a foam product with structured or reduced, whereby when heated a sub-15 ured surface is achieved by introducing a blowing agent of different degrees of expansion and thus a surface structured in a foamable resin batch and subsequently structured, characterized by heating a layer of the resin batch to a one in the specific temperature at which the blowing agent foamable resin mixture decomposes a metal compound and causes the resin mixture to foam, as a catalyst for lowering the decomposition 20 where one introduces before heating to sections of the temperature of the blowing agent and that of the mentioned layer applies a substance which either increases or decreases the substance-applied to sections of the resin composition decomposition rate of the blowing agent at the sections relating to a chelating agent for the metal of the catalyst with a chelation constant of at least, whereby the E scratch is a different 1 · 10 ⁴ . 35 degree of swelling achieved and thus a structured upper 2. The method according to claim 1, characterized in that the marked surface is generated, which method is drawn by that one is identified as a metal chelating agent 2-mer, that one in the foaming captobenzothiazole, alizarin, Ν, Ν'-disalicylidene resin formulation a metal compound as a catalyst 1,2-propanediamine. α-Nitroso - /? - naphthol, 1,8-di- to lower the decomposition temperature of the expanded hydroxyanthraquinone and / or acetoacetanilide 30 by means of introducing and that the resin is used on portions, mass applied substance a chelating agent for the 3. The method according to claim 1 and / or 2, the metal of the catalyst having a chelation characterized in that the metal in the as a constant of at least 1-10 ⁴ is. Metal compound used as catalyst lead, the foam product produced according to the invention Zinc, cobalt, tin, aluminum, cadmium and / 35 has similar properties to that described in DT-AS 15 00 406 or nickel. bene product has a surface that is embossed Seems to be provided as the areas on soft the chelating agent was applied, deepened compared to the fully foamed areas 40 appear. The surface of the product can be covered with a full, wear-resistant layer The invention relates to a method for producing the by placing a non-foamable second layer of foam products suitable as decorative materials or coating of a resin mixture over the structured surface. foamable layer is applied. There are already various processes known for producing simple processes for producing foam production of foam products with structured products with a practically thick, wear-resistant surface, in which no embossing rollers are used. According to FR-PS 12 70 669 are shown. According to a modified embodiment, surface reliefs on foam masses produced by the inventive method can be chelated by printing at least two foamable training agents on a base layer, or otherwise applying masses with different blowing agent content and then the foamable composition, which is imprinted on a base in an image-wise distribution, foams onto this base and foams by heating. This process layer can be applied. The foamable accessory requires precisely working devices and a composition can also be formed into a solid or multiple foam batches, which can be formed with a costly mixture, in that it is connected with excessive technical effort. Bringing the chelating agent is heated. If it is expensive, the US Pat. No. 2,920,977, another optional process, can be known processes in which products with a structured application of the wear-resistant or abrasion-resistant surface are produced by applying a layer after decomposition of the blowing agent and the surface of a substrate thick layers of 60 fusion of the foam layer can also be omitted foamable approaches with different amounts. The wear layer can then be deposited on any blowing agent. Manner, for example by spraying, coating. US Pat. No. 2,825,282 describes a process for producing with a film or the like. In contrast to foam products with a structured upper - if desired, the wear layer can also be omitted by introducing a blowing agent into a 65, if a product with a limited foamable resin formulation and subsequent wear resistance is desired,
heating of this approach described, in which the same measures as in accordance with the invention can be used to differentiate the extent of heating according to the invention on the surface