DE2832343A1 - SELF-ADHESIVE COMPOSITE OBJECT, METHOD OF APPLICATION AND COMBINATION OF SUBSTRATE AND OBJECT - Google Patents

Description

Our no. 21 982 Pr / br

Stauffer Chemical Company Westport, Conn., V.St.A.

Self-adhesive composite article, method of application thereof and substrate and article combination.

The invention relates to a self-adhesive, made of plastic film and flexible underlay existing object, which is suitable, for example, as a roofing material for vehicles, a method for its application to a desired substrate and the resulting combination of substrate and object.

Composite objects made of plastic film and flexible base, which can be used, for example, as roofing material for vehicles, e.g. automobiles are well-known products. Such composite materials have other uses as well purposes such as padded vinyl wall coverings, lining materials for automobile trunk spaces, etc., however in the present in connection with their main commercial use, namely as roofing material for motor vehicles as described by automobiles.

Such composite articles, when used as vehicle roofing materials, have been conveniently attached the vehicle manufacturer sells without an adhesive layer, and the The manufacturer then marked the exposed side of the backing material with a solution of a contact adhesive in the vehicle

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factory and then attached the sprayed composite item to the vehicle substrate, which was also used with the the same adhesive had been covered (see US Pat. No. 3,935,353). Contact adhesives are adhesives that apply to both surfaces to be bonded must be applied. They cannot be called "self-adhesive adhesives" as used herein are designated. Such a technique suffers from a number of serious disadvantages. Spraying glue on Solvent base in the vehicle factory can pose potentially serious environmental / safety / health problems. the Technology is quite time consuming and requires the use of more manpower than is desirable. The spraying Adhesive on the backing can also lead to an uneven and discontinuous adhesive coating on the backing Guide underlay, forming cavities between the underlay and the vehicle roof, which raise corrosion Schwxerxgkexten can when the finished vehicle is in actual use.

An alternative to this conventional process is described in U.S. Patents 3,846,200 and 3,935,353. In these patents a product made of plastic film and flexible backing is proposed, which has a layer of a non-adhesive, heat-activated Has adhesive. Such a product also has certain disadvantages, although it does have some of the disadvantages of the overcomes common factory spray techniques. One of the major drawbacks is the need for heating devices in the area where the automobiles are assembled to heat the adhesive to its heat activated temperature at which the stickiness occurs. This can require additional undesirable capital investments for the vehicle manufacturer. aside from that In such a technique, the plastic sheet material must be preformed with heat prior to application in a press

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ensure a correct fit.

With the invention, for use, for example, as Self-adhesive composite article roofing material suitable for vehicles addresses these disadvantages as described above for adhesives sprayed on with solvent, contact adhesive constructions and constructions that have a hit-activated Glue included, overcome when used to form such roofing materials. It contains a plastic wrap that comes with the document material is connected, which is an essentially coherent and. even layer of pressure sensitive adhesive has on the side on which there is no plastic film, and in which, in a preferred embodiment, the exposed surface of the adhesive layer is covered with a release liner to protect this layer from contamination protection. The invention also relates to a method for attaching such a laminate to a desired one Substrate, for example a vehicle, only by applying pressure and it also relates to the combination of substrate and composite object.

The composite article according to the invention has in the Use as a vehicle roof material has the following main advantages compared to the known use of sprayed-on solvent adhesives: Avoidance of potential environmental / Safety ZHealth hazards associated with spraying Potential toxic solvents in the workplace are linked, saving time and manpower that sum up of the item on the vehicle are required and better protection against corrosion of the combination of composite Object and vehicle due to the presence of a substantially coherent and uniform layer of adhesive in the subject matter according to the invention, whereby a substantially coherent and uniform surface for the Contact with the substrate is established.

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The object of the invention has when used as Vehicle roofing material versus the use of a heat-activated one Adhesive as shown in U.S. Patents 3,846,200 and 3,935,353 will have the following main advantages: to create an adhesive connection Achieving between the object and the vehicle substrate is to heat the object after it has been applied on the vehicle not required and the deformation of the object in a heated press is not necessary.

The drawings serve to further explain the invention:

Fig. I is an enlarged cross-section is an object of the closest prior art _s wherein the non-cohesive layer β of a non-adhesive contact adhesive is shown after the adhesive has been sprayed in a vehicle factory on the base 3, and

Figure 2 is an enlarged cross-section of a preferred embodiment of the invention, wherein the release layer 8 is just separated from the continuous and uniform layer of the Adhesive 7 is peeled off in preparation for attaching the composite article to a desired substrate, e.g. a vehicle roof.

The composite article of the present invention includes some Elements that are old, namely the plastic film 1 and the flexible base 3, which is attached to the film 1. A suitable glue 2, ζ 3 ·. a plastisol adhesive, can optionally can be used to attach the plastic film © 1 to the base 3, this adhesive sometimes being used for known ones Foil l / underlay 3 items is used. Every average

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a skilled person would be able to find the appropriate materials for the production of such a film / underlay sub-combination (possibly connected with adhesive) according to the following Manufacture description.

The plastic sheet 1 can be made of any thermoplastic or thermosetting synthetic polymer that

is preferably weather- and UV-resistant in order to give the assembled object a long service life if ey should be attached to a vehicle and used as a roofing material. Representative plastic sheet materials include vinyl and vinylidene, acrylic, urethane, polyester, fluorocarbon, and polyolefin polymers, and compatible mixtures thereof. Vinyl chloride polymers are preferred for economic reasons. Preferred vinyl chloride polymers may be any of the conventional polyvinyl chloride resins heretofore used for such purposes, in combination with any desired suitable plasticizers, fillers, stabilizers, pigments, fungicides, processing aids and the like external plasticizers are used. The thickness of this plastic sheet is generally from about 0.13 to about 0.7 mm, although thinner or thicker sheets can be used as desired. The film can be made by any known technique and is generally embossed with a suitable decorative pattern. It can be covered with a thin protective polymeric coating (not shown) such as urethane, acrylic, or vinyl polymers, or compatible mixtures thereof, to protect it from damage due to mechanical, chemical, or environmental factors.

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The film 1 is connected to the base, which is designated as reference number 3 in the figures. The connection between the underlay 3 and film 1 can be done with the aid of a thin layer of adhesive 2, or the film can be connected directly to the base 3 be (e.g. by laminating or calendering the hot plastic film 1 on the base 3) so that the connection takes place without an intermediate adhesive layer is required.

The backing 3 can be made from a wide variety of conventional backing materials such as nonwoven, woven, knitted or composite materials (nonwoven / foam combinations, nonwoven / knitted combinations, nonwoven / woven / knitted combinations, etc.) to provide a sufficiently thick layer which helps camouflage any surface irregularities that may exist on the substrate, such as a vehicle roof, when the composite article is on the substrate. The term "base" as used in the present context relates to those base materials which are used for the production of composite objects from film and base, for example as exterior roof materials for vehicles. In general, the weight of the backing material is about 68 to 680 g / m and its density is about 32 to 320 kg / m. The thickness of the composition and base film is generally about 0.5 mm to 5.1, preferably about 1, I ¹ mm to about 2.2. _.

Preferred backing materials are the commercially available ones because of their improved ability to cut the finished product to size Underlays made from a non-woven fabric made of synthetic fibers that are needle-punched into a thin layer of foam. Some preferred Examples of fibers that can be used in such bases are polypropylene, rayon, polyester, acrylonitrile, nylon,

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Polyphenylene sulfide and mixtures thereof. To suitable usable Show materials include urethane and polyvinyl chloride foams. The denier of such fibers in this type of backing can be be between about 1 and about 20. "Denier" means a unit of fineness that is equal to the fineness of yarn, that weighs 1 gram per 1000 meters. The "foam in such a pad may have a thickness of about 0.25 to about 2.5 mm.

The base 3 is preferably made water-repellent by treatment with an effective amount of at least one *; common water repellant when the composite article of the present invention is to be used outdoors, for example as a vehicle roofing material. Fluorocarbon emulsions available under the trade designation "Zepel" (from EIDuPont de Nemours Go.) Or "Scotchguard" (from 3M Co.) are representative types of materials that can provide such water repellency. To excluded 'selected type of backing material to behändeIn _3, it may, for example, done in a Fluorkohlenstoffbad and are dried and the resulting product be cured. The product resulting from either this or alternative conventional treatments will persist when exposed to water, oil or other contaminants. Further information on how the pad 3 can be made water-repellent can be found in "Waterproofing and Water Repellency", Kirk-Othmer Encyclopedia of Chemical Technology, 2nd Edition, Vol. 22, pages 135 to 156 (1970).

Optionally, one or more corrosion inhibitors can be used to treat the substrate 3, if the object is to be used outdoors in order to impart corrosion protection to the object / substrate combination or the same to increase. The corrosion inhibitor can be any compatible

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Be an inhibitor and can be added together with the aforementioned water repellent. For example, if a Fluorkohlenstaffbadbehandlung _s is applied to such prior art corrosion inhibitors such as nitrites are present ₃ phosphates, chromates and sulphates in the bathroom to ien-wirl as corrosion inhibitors to when the final combination produced from the subject substrate is to be used outdoors /. A corrosion inhibitor that is preferred for economic reasons is sodium nitrate. Further. Information about _s can be treated as the base 3 to -the combination of object / substrate corrosion moor, tons of "Corrosion Inhibitors" _s Kirk-Othmer Encyclopedia of Chemical Technology, 2nd Edition, Volume 6, pages 317-346 (1965 ) removed v / earth.

The well-known in the art composite article of foil 1 and base 3 can be prepared by a variety of known methods, such as direct or laminating Kalanderschichtung _fl subsequent layering or pouring.

Direct Kalanderschichtung or laminating generates a composite die did blessing state without using the adhesive layer 2. The plastic film 1 acts as an adhesive _s because they vrird brought shortly after their formation in contact with the base 3, while the film 1 is still hot and sticky.

The subsequent lamination is another well-known method and is different from laminating or direct Kalanderschichtungsteciiniken characterized _s that the plastic sheet 1 not usually formed immediately before the Verklebestufe and that an adhesive layer 2 with the aid of known Besehichtungsmethoden (gravure _cylinder's doctor blade, Orphan or ümkehrwalae) directly on the fo-

Lie is applied before the film comes into contact with substrate 3. A roll of preformed film is generally the film source, with a thin layer of adhesive being applied to the side of the film to be bonded to the backing. The adhesive is applied by suitable devices generally in an amount of about 3 ^ to about 170 g / m ² depending on the adhesive. The coated film is then brought into contact with the backing to form the composite article known in the art.

Adhesives that are suitable for the post-layering technique are known in the art. Some examples are plastisol, epoxy, acrylic, and urethane adhesives. Plastisols are among the most popular materials. These are dispersions of finely divided polymeric materials in non-volatile organic liquids and low-melting solids, which are generally referred to as plasticizers. Suitable plasticizers are phthalate, adipate and sebacate esters and polyols such as ethylene glycol and its derivatives. A typical plastisol composition consisting of 50 parts of polymeric material and 50 parts plasticizer that form due to the solvation of the resin particles by the plasticizer a paste which forms a gel when heated to about 150 ⁰ C and melts. If a volatile solvent is contained in * m plastisol, then the adhesive is generally referred to as an organosol, which is also suitable for use in accordance with the invention.

To produce the finished self-adhesive according to the invention When the object is assembled, the side of the substrate 3 lying on the surface is essentially connected to one another Layer 7 of a suitable tacky pressure sensitive adhesive coated. Pressure sensitive adhesives are a well known class of adhesives and are evolving

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Maximum adhesive bond through the application of pressure alone. Preferred Adhesives in this class are those that have good adhesion and, if the item is to be used outdoors, durability exhibit outdoors. Self-crosslinking thermosetting Acrylic pressure-sensitive adhesives are a preferred class that can be used to make the laminate according to the invention. Examples for patents describing these adhesives are U.S. Patents 3,269,994, 3,579 W, and 4,005,247. Preferred formulations are under the trade name "Aroset IO85" (Ashland Chemical Company), "Bostik 7525" (USM Corp.), and "DC-7025" (Daubert Chemical Co.). These adhesives also have particularly good compatibility with substrates that contain the above-described water-repellent agents and / or Corrosion inhibitors included. The thickness of these adhesive layers in the composite article of the invention can be from about 0.01 to about 0.25 mm. The shift will applied to the base 3 so that it forms a substantially coherent coating, which is also substantially is free of cavities, channels and the like. The presence of such a layer creates a barrier between the substrate and the atmosphere, humidity and other environmental factors that can cause corrosion when the article is used as a substrate / article combination outdoors will.

The composite article of the present invention can be used without the presence of release liner 8, for example if it is used shortly after the adhesive layer has been applied, care must be taken to avoid contamination of the outer surface of the adhesive layer 7 with foreign matter. If you want this embodiment of the invention, the Adhesive in the form of a viscous liquid can be poured onto the base 3 and dried by applying heat. For the

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however, most end uses will be the compound Article with a suitable peel-off layer 8 is manufactured by the manufacturer and the product is sent to the consumer for use sent.

The release layer 8 can be any release layer known to those skilled in the art for the manufacture of self-adhesive products ^with removable, water-soluble protective coatings. A preferred sheet material is silicone-coated release paper with a thickness of about 0.05 to about 0.25 mm. Polyolefins (e.g. from ethylene), ethylene / vinyl acetate copolymer, ethylene / acrylic copolymer and ethylene / chlorinated polyethylene mixtures, suitably coated with a release liner, such as a silicone release agent, can also be used as the release liner.

A preferred method of applying the foils / documents 3-combina- "' tion and to attach the pressure-sensitive adhesive layer 7 and release layer 8 together consists of the transfer layer (transfer lamination). In such a process, a solvent solution, an aqueous dispersion or a hot melt of the Adhesive layer 7 applied to the peel layer 8 and the thereby resulting composition (except when a hot melt technique is applied) heated to dry the adhesive layer 7. The adhesive side of this adhesive / release liner laminate is then coated onto the exposed surface of the backing 3, preferably in a hot nip for laminate production in order to produce the product shown in FIG result. The use of a hot roller gap provides a good bond between the adhesive layer 7 and the base 3 sure, those with water repellants and / or corrosion inhibitors may have been treated.

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In addition to making the transfer laminate, the adhesive onto the document by using the usual direct application method can be applied using either doctor blade, roller, reverse roller or lamination techniques, provided that an essentially coherent and uniform layer of the pressure-sensitive adhesive is thereby created.

When the composite article of the present invention is to be used, the adhesive layer 7 is in contact with the vehicle substrate and, when it's in the right place, pressure is applied to keep it secure to your vehicle to fix. This procedure is carried out without Solvent-based adhesives are sprayed on or the laminate / vehicle substrate combination is heated.

The following examples serve to further illustrate the invention.

example 1

This example illustrates the manufacture of a preferred composite article of the present invention. The first step for preparing the desired product was that one contained at a temperature of about 335 ° C, a film formulation containing the following components, calendered to a thickness of about O ₃ 36 mm.

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Component wt. -%

Polyvinyl chloride homopolymer resin ^ 7,

Calcium carbonate filler 14.328

normal alkyl phthalate plasticizer 31.19 ¹ J

Pungicide / plasticizer stabilizer 1.197

epoxidized soybean oil 2,385

colloidal silica 0, ^ 77

Heat stabilizer (metal soap) 0.100

Pigment 0.900

Barium / Cadmium / Zinc Stabilizer 1.197

liquid phosphite stabilizer 0, ^ 77

The calendered film was then applied using a knife-roller method a coating of a polymeric solution is applied at a rate of 0.57 kg / m. The fleeting one Solvent in the coating solution was evaporated in a drying oven at a temperature of about 71.1 ° C and without getting into the Environment to be drained regained. The following components formed the coating:

Component wt. -%

Methyl ethyl ketone 89.11

PVC homopolymer resin 7.61

Acrylic resin 2.70

colloidal silica 0.58

The coated vinyl sheet was then coated onto a nonwoven substrate with a plastisol adhesive and was sealed with a decorative grain at a temperature of around 160 ° C, which temperature also hardened the plastisol adhesive.

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The nonwoven substrate was a full-polyester mixture of 60 wt .- #, 3 denier, 10.2 cm staple fibers j 20 wt -.% _S 6 denier, 7.6 cm staple fibers and 20 wt -.% "6 denier, 15 _S 2 cm staple fibers which had been needle punched into a polyester urethane foam with a thickness of 0.8 cm and a density of 32 kg / nr. The nonwoven / foam construction had been treated with fluorocarbon. It is a commercially available product from Poss Manufacturing and weighed 0.22 kg / m. The 0.8 cm foam was predominantly on one side of the substrate, the side that was coated onto the vinyl sheet.

The pressure-sensitive adhesive formulation contained the following components:

Part by weight?

self-crosslinkable acrylic pressure-sensitive adhesive solution (Aroset IO85)

Ethyl acetate solvent toluene solvent

The composition was reverse roll applied at 0.16 kg / m onto HP Smith Inc. polyethylene coated 43ig / strip kraft release paper. The solvent was evaporated in a drying oven at 65 to 15O ⁰ C and recovered. After drying, the release paper / adhesive composition was coated onto the nonwoven side of the nonwoven / vinyl film composition. In order to achieve the desired degree of penetration of the adhesive into the nonwoven backing, steel nip roll was heated at the laminate station at 85 ⁰ C and pressed against the release paper.

77 , 77 16 , 67 5 , 56

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Example 2

Example 1 was repeated for an assembled article but used as the pressure sensitive adhesive a commercially available adhesive from Daubert Chemical Company (DC-7025), which was used without dilution by adding more solvent.

Example 3

The procedure of Example 1 was used to prepare a composite Article, but used a commercially available adhesive from USM Corp. as the pressure sensitive adhesive. (Bostik 7525), which was used without dilution by adding another solvent.

For: Stauffer Chemical Company Westport, Conn., V.St.A.

Dr H.J. Wolff Lawyer

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Claims (17)

BEIL, WOLFF & BEIL July 21, 1978 RECHTSANWÄLTE ADELONSTRASSE 58 2 8 3 2 3 A 3 6230 FRANKFURT AM MAiN 80 Patent claims: 1. Self-adhesive composite article containing (a) a plastic sheet, (b) a thick pad attached to one side of the film and (c) a substantially contiguous and uniform layer of pressure sensitive adhesive that overlaps that of the plastic sheet opposite side of the pad is glued. 2. Product according to claim 1, characterized in that the film is a vinyl chloride polymer. 3. Product according to claim I _9, characterized in that the film has a thickness of about 0.13 to 0.7 mm. 4. Product according to claim 1, characterized in that the film is connected to the base by an adhesive layer. 5. Product according to claim 4, characterized in that the adhesive is a plastisol adhesive. 6. Product according to claim 1, characterized in that the base is a nonwoven fabric. 7. Product according to claim 6, characterized in that the nonwoven also contains a foam layer. 8. Product according to claim 1, characterized in that the weight of the base is from about 68 to about 680 g / m 2. 809888/0874 ORSGSHAL SHSPECTED -μ. 9. Product according to claim 1, characterized in that the Density of the substrate is from about 32 to about 320 kg / m ^. 10. Product according to claim 1, characterized in that the pressure-sensitive adhesive is an acrylic pressure sensitive adhesive. 11. Product according to claim 1, characterized in that the adhesive has a thickness of about 0.01 to about Q _S 25 mm. 12. Product according to claim 1, characterized in that it also contains a release liner. 13 · Product according to claim 12, characterized in that the The backing has a weight of about 68 to about 680 g / m 2 and a density of about 32 to about 320 kg / m · ^. 1 * 1. Product according to Claim I _3, characterized in that the base has been treated with a water-repellent agent and a corrosion inhibitor. 15.Product according to claim 1, characterized in that the thickness of the film and the base is about 0.5 to about 5 ₃ 1 mm. 16. Method of attaching a self-adhesive composite Object, characterized in that one (a) a product of any one of claims 1 to 11 or 13 is applied to the substrate and (b) only applies pressure to the product and substrate. 17. Combination of firmly connected substrate and a product of any one of claims 1 to 11 or 13 to 15 · 809S8S / 0874