MXPA97006018A - Articles that incorporate adhesives sensitive to lapresion, which have improved adherence to polyvinyl plastify chloride - Google Patents

Abstract

The present invention relates to articles comprising a substrate, preferably a retroreflective layered material, having a coating of a pressure-sensitive adhesive composition, and in addition to articles wherein the adhesive adheres the substrate to a component with Highly monomeric and monomerically plasticized PVC, preferably a fabric coated with PVC. The adhesive comprises a crosslinked copolymer of a monofunctional acrylate first ester of a non-tertiary alcohol having a homopolymer, a glass transition temperature of less than -25 ° C, a nitrogen containing moderately basic monomer therewith selected from the group consisting of N , Substituted N-dialkyl amides, an optional copolymerizable acidic monomer, a monofunctional acrylate second ester, optionally of a non-tertiary alcohol having as a homopolymer, a glass transition temperature of -25 [deg.] C. or higher, and a crosslinking agent. The invention also relates to a method for joining a highly and monomerically plasticized PVC component to a substrate, preferably a retroreflective layer material, using the adhesive.

Description

ARTICLES THAT INCORPORATE PRESSURE SENSITIVE ADHESIVES, WHICH HAVE IMPROVED ADHERENCE TO PLASTICIZED POLYVINYL CHLORIDE Background of the Invention 1. Field of the Invention The present invention relates in general to signaling articles such as retroreflective and non-retroreflective articles. More particularly, the invention relates to pressure sensitive adhesives that allow excellent adhesion of base, retroreflective and non-retroreflective substrates to surfaces such as polyvinyl chloride coated, plasticized, highly monomeric fabric, as may be frequently used in fabrics for cover.

Related Technique In the article "Truck Cover Market Report", Data Textile, May 1991, distinguishes between cover fabrics and truck covers. A REF: 25215 truck cover is defined as a tight cover or a cover specifically designed for use on the open top of a dump truck or tow truck platform, and strictly differs from a deck cloth per se , since the cover fabrics are not usually adjusted for any particular use. For the purpose of the present invention, the terms are interchangeable. As discussed in the request of the Patent Cooperation Treaty (PCT) No. WO 93/10985, published June 10, 1993, cover fabrics usually consist of a fabric coated with a plastic material. The fabric, although not required in all cases, is usually a woven polyester or nylon, which may have a weft insertion. The plastic material is typically selected to be tough and flexible, and thus plasticized polyvinyl chloride (PCV), polyamides (such as nylon and aramid), and polyprene (such as chloroprene rubber) are commonly employed. Roofing fabrics are used for many roofing purposes, for example, within the construction industry, and in particular to cover trucks. These are also used to make larger tents, for example, for use in temporary military sites and camps for refugees as well as for public events. As further established in the PCT application mentioned above, it is a common practice to print logos, company names, advertising phases or slogans, instructions and other decorations on truck cover fabrics, for informational and advertising purposes. Reflecting decorations are particularly advantageous, making the trucks visible at night. A solution to the problem is described in the PCT application mentioned above, which describes a cover fabric comprising a fabric coated with a plastic material, preferably PVC, polyamide, or polypropylene, provided with a decoration of a reflective material, fixing (with a flexible, transparent, covering film) a reflective layer to a piece of the fabric fabric of cover fabric, intermediate, whose coating is of the same type as (or is compatible with) that of the cover fabric, by means of the high-frequency welding or application of heat, and then apply the piece of the woven fabric of the cover fabric, intermediate, provided with a reflective layer and a flexible, transparent, superimposed film, optionally formed in the desired shape, to the fabric for covered by melting with hot air. Fabrics coated with PVC differ mainly in the type and amount of plasticizer added to PVC. A commercially available PVC coated fabric has been analyzed which contains up to 42 weight percent of monomeric low molecular weight plasticizer. These monomeric low molecular weight plasticizers tend to migrate to the surface of the PVC coated fabric, and tend to cause problems in PVC-coated fabric adhesion materials with pressure sensitive adhesives (PSAs). Acrylic PSAs generally comprise a primary component of acrylate or methacrylate monomer or a combination of monomers of this -e that, when polymerized, have a low glass transition temperature (Tg) and low modulus. (ie, these are with properties like rubber and soft). These sticky, soft low Tg monomers are typically copolymerized with a secondary component consisting of high T3 monomers usually polar monomers such as acrylic acid, methacrylic acid, itaconic acid, acrylamide, methacrylamide, and mixtures thereof. As described in U.S. Patent No. Re 24,906 (Ulrich), when such polar monomers are incorporated with a predominance of low Tj monomers, a sufficiently tacky, pressure sensitive adhesive having high cohesive or internal strength is formed. In addition, the increase in cohesive or internal strength (ie, shear), which is often required to withstand the severe environmental and chemical conditions encountered in transportation applications, can be obtained through crosslinking. An approach to reduce the tendency of monomeric plasticizers to migrate out of the highly and monomerically plasticized coated PVC fabric and into the bound PSA is to drive the adhesive with the plasticizer, thereby reducing the mass transfer gradient for the migration of the PVC plasticizer in the adhesive. Such an approach was taken in U.S. Patent No. 4,946,742 (Landin), which typically describes stickiness and pressure sensitive adhesives having excellent long-term adhesion to plasticized vinyl surfaces, prepared from a representative mixture of the dioctyl phthalate plasticizer and a terpolymer of an alkyl acrylate, a nitrogen containing vinyl monomer and a vinyl carboxylic acid. However, the addition of the plasticizer to the adhesive is added to the cost of the adhesive, and requires an additional process step. Furthermore, if the plasticizer present in the PVC coated fabric is different from the plasticizer present in the adhesive, a driving force still exists for the plasticizer present in the PVC coated fabric to migrate in the adhesive due to the concentration gradient. The development of an unplasticized PSA allows all manufacturers to apply material in reterorreflector layers of the cube-corner type and other types on PVC-coated fabrics, monomerically plasticized, thereby reducing or eliminating the need for thermal bonding methods and by plasticized PSAs.

European patent application No. 615 983 A2, published on September 21, 1994, discloses a PSA having dominant ability to bind to acidic, solid surfaces such as automotive paints, resistant to acid rain, acids and PVC, and to remain firmly attached thereto, comprising (a) about 60 to about 90 parts by weight of at least one monomer selected from the group consisting of (meth) acrylate, unsaturated, monofunctional esters of non-tertiary alkyl alcohols and mixtures of the the alkyl groups of which comprise from about 4 to about 12 carbon atoms which, like the homopolymers, have glass transition temperatures below about -20 ° C; (b) correspondingly, about 40 to about 10 parts by weight of a basic monomer copolymerizable with the monomer of element (a); (c) about 0 to about 3 parts by weight of an acidic monomer copolymerizable with the monomers of the elements (a) and (b) wherein when the acidic monomer is included, the basic copolymerizable monomer must be present in a molar excess; and (d) about 0.05 to about 1 weight percent crosslinking agent based on the total weight of (a) plus (b) plus (c). Representative examples of copolymers described herein are copolymers of isooctyl acrylate (low Tq monomer), acrylic acid and a basic copolymerizable monomer that can be selected from strongly basic monomers., moderately basic and weakly basic. Although this work has a power to attract attention, the use of the PSA compositions described herein has not been described or suggested by the joining of a variety of materials, as used in reflective signaling articles and not reflectors, to surfaces of highly PVC and onomerically plasticized. PCT Application No. WO 94/19711, published September 1, 1994, describes a retroreflective structure in which an array of retroreflective prisms is formed, freestanding on a substrate for the application of the structure to pre-existing structures formed of compatible fabrics, such as cover fabrics. The structure employs a non-pressure sensitive adhesive that requires time to cure, such as a wet-curable polyurethane adhesive component, to adhere the freestanding prisms to the substrate, and thus the structure requires pre-assembly. It would be advantageous if the pressure sensitive adhesives lacking plasticizer could be used to adhere a retroreflective and non-retroreflective material to highly and monomerically plasticized PVC surfaces.

Brief Summary of the Invention In accordance with the present invention, the articles are presented using a selected class of acrylate adhesives, some of which were described in the published European patent application, mentioned previously of the assignee, for adhering a variety of materials (such as films). of sealing material of retroreflector layers in the form of a corner of a cube, wherein the sealing film is made using a variety of polymeric materials, for example polyurethane, polyester and polyvinyl chloride films, and / or directly to cube corners made of acrylic or polycarbonate polymers, or cube-shaped corners made of acrylic or polycarbonate polymers, or metallized bucket corners, or other types of material in retroreflector layers (such as layered materials, with spheres) and non-reflective base layer materials ) to a highly monomerically plasticized polyvinyl chloride (PVC) component, with sufficient resistance to peeling of the coating, resistance to static shear stress and tolerance to the plasticizer and moisture to pass at least three, preferably all the required tests of such signaling articles. As used herein the term "PVC component" includes fabrics coated with PVC and PVC articles devoid of fabric. Highly and monomerically plasticized PVC components, particularly preferred are PVC coated fabrics. In particular, an aspect of the invention is an article comprising: (a) a layer of pressure sensitive adhesive, comprising a crosslinking copolymer of 100 parts by weight of monomer of elements (i), (ii), (iii) and optionally (iv) wherein the copolymer comprises: (i) about 50 to about 90 parts by weight (more preferably about 60 to about 80 parts by weight) of at least one monomer selected from the group consisting of a first functional mon acrylate ester of a non-tertiary alkyl alcohol, and mixtures thereof, the alkyl group of which comprises from about 4 to about 12 carbon atoms, which as a homopolymer has a glass transition temperature less than -25 ° C; (ii) about 10 to about 25 parts by weight (most preferably about 14 to about 20 parts by weight) of a moderately basic, copolymerizable monomer (ie containing an ethylenically unsaturated group) selected from the group consisting of N, Substituted N-dialkyl amides (the N, N-dialkyl amide substituted moderately basic, copolymerizable, preferably selected from N-vinyl pyrrolidone, N-vinyl caprolactam, and monomers within the general formula (I): CH2 = C-Z (i) Wherein: R is selected from the group consisting of -H and -CH3; Z is -C (= 0) NR: R2; R1 and R2 are independently selected from the group consisting of alkyl groups having from 1 to 10 carbon atoms); (iii) about 0 to about 7 parts by weight (more preferably about 3 to about 6 parts by weight) of an acidic monomer copolymerizable with the monomers of elements (i) and (ii) where when the monomer acidic is included, the basic, copolymerizable monomer is present in a molar excess; (iv) 0 to about 30 parts by weight of a second monofunctional acrylate ester of a non-tertiary alcohol having a homopolymer of a glass transition temperature equal to or greater than -25 ° C; and (v) approximately 0.01 a about 1 weight percent of a crosslinking agent based on the total weight of (i) plus (ii) plus (iii) plus (iv), wherein the relative amounts of the monomers are selected such that the item passes at least three (preferably four, most preferably all) tests selected from the group consisting of a pressure wash test after soaking in water, a pressure wash test after thermal conditioning, a static (initial) shear test and after thermal conditioning, a T-peel test of the coating (initial), a T-peel test of the coating after thermal conditioning, and a T-peel test of the coating after soaking in water (these tests are described more fully herein); and (b) the adhesive layer coated on a substrate. Preferably, the adhesive is used to adhere a highly monomerically plasticized PVC component, preferably a PVC coated fabric, to the substrate. The substrate layer is preferably selected from the group consisting of i) a sealing film (preferably polyurethane, polyester, polyvinyl chloride or polycarbonate) bonded to a retroreflective, transparent, layered material having a substantially flat surface and a second structured surface, the second structured surface comprises a plurality of notches defining a plurality of peaks, ii) a retroreflective, metallized, layered material having a substantially planar surface and a second structured surface, the structured surface having a metal layer thereon, iii) surface not incident to light from a retroreflective layer material, with spheres (ie, materials in retroreflective layers comprising a plurality of transparent microspheres), and iv) other non-retroreflective substrates , such as polymeric films including polyurethane films, films d polyolefin, and plasticized vmilo films (as described in U.S. Patent No. 4,605,592 (Paquette et al.)) or soft metal films such as aluminum. In one embodiment of the retroreflector article of the invention, the article can be attached to a fabric coated with PVC using thermal methods, such as high frequency welding, hot air fusion and the like. This is useful when it is desired to add materials in retroreflective layers to be used or old cover fabrics, or when repairing worn or torn cover fabrics. Another aspect of the invention is a method of bonding a highly and monomerically plasticized PVC component to a substrate, the method comprising the steps of: (a) formulating an adhesive composition as described in reference to the inventive signaling article; (b) applying the adhesive composition to either a highly monomerically plasticized PVC component, a bonding surface (i.e., a surface opposite the non-reflective surface) of a substrate, or both; and (c) joining the surface of the substrate with the PVC component, the adhesive composition placed between the PVC component and the substrate binding surface, wherein the substrate binding surface is defined by previously mentioned substrates. A major advantage of the method of the invention, particularly when the retroreflective substrates must adhere to truck cover fabrics as signs or visibility marks, is that the user can easily apply the retroreflective sheet material to the cover fabric without any tools additional, such as high frequency welding machines and hot air fusion.

The additional aspects and advantages of the invention will become apparent from the following description of the invention.

Brief Description of the Drawing FIGURE 1 is a cross-sectional (elongated) view of an illustrative article of the invention, comprising the retroreflector article in the form of a cube corner adhered to a PVC component using an adhesive as described herein; FIGURE 2 is a cross-sectional (elongated) view of an illustrative article of the invention, comprising the metallized layer of a cube corner-shaped retroreflective article adhered to a PVC component using an adhesive according to the invention; and FIGURE 3 is a cross-sectional (elongated) view of an illustrative article of the invention comprising a retroreflective substrate of internal lenses adhered to a PVC component using an adhesive according to the invention.

These figures are not to scale and are proposed to be illustrative and not limiting.

Description of Illustrative Modalities The invention provides a retroreflective article comprising a highly monomeric PVC component plasticized by a pressure sensitive adhesive (PSA). The articles of the invention, mainly by virtue of the adhesive, undergo at least three rigorous tests, and preferably all tests, described further herein, which are used to determine whether the articles resist shear after soaking in water. , the static shear stress after thermal conditioning, pressure washing and the like, in a real world environment. Many previously known adhesives have not shown the ability to meet at least three of these tests. Before discussing these tests and the pressure sensitive adhesives, however, the inventive articles are described with reference to the figures in the drawing.

Retruereflective Items A. Items that incorporate the material in retroreflector layers in the form of cube corner. A preferred embodiment of the articles of the present invention relates to a retroreflective article comprising a retroreflective, transparent layered material having a first substantially planar surface and a second Structured surface, the second structured surface comprised of a plurality of notch assemblies defining a plurality of peaks (in the cube corner-shaped layer material, typical at least three sets of intersecting parallel notches l ', while in FIG. the prism films an individual set of parallel notches is typical), a layer of sealing film (colored or uncoloured) placed on, and attached to a first portion of the notches, a The second portion of the notches prevents contact with the sealing film layer, and a layer of pressure-sensitive adhesive (as described herein) placed between the sealing film layer and a highly PVC component. monomerically plasticized.

As used herein, the term "peak" means a projection having at least two planar faces, such as prisms, pyramidal protrusions, cube-corner protrusions, and the like. The phrase does not include protrusions that do not include flat facets, such as the protrusions present in holographic films. The term "transparent, retro-reflective layer material" means a layered, plastic material that transmits at least 90% incident light in the visible spectrum (approximately 400 to 700 nanometers wavelength), as determined by a standard spectrophotometer. Referring now to the Figures, where similar numbers are used to represent similar elements from figure to figure, a preferred embodiment of a transparent, cube corner retroreflective article of the invention is illustrated in cross section (elongated) in FIGURE 1. In FIGURE 1, the layered material 100 comprises a transparent layer 2 having a smooth, flat surface 4 and a structured surface 6 comprised of a plurality of peaks 8. The layer 2 can be extremely thin to increase the flexibility, or the superimposed layer 13 may have a low modulus as described in the co-pending assignee patent application Serial No. 08 / 326,696, issued October 20, 1994. In this application, the layer 2 is formed from a superimposed layer, thermoplastic film 13 and thermo-hardened, uncoupled cube corner elements. A thermoplastic sealing film layer 10 is placed on the peaks 8, and a plurality of air spaces 12 is defined between the sealing film layer and cube corners 10 to impart retroreflectivity to the article. The sealing film layer 10 adheres to the layer 2 in a plurality of sealing areas., wherein the thermoplastic sealing film material has flowed between the individual corner corner elements to reach and merge with the superimposed, thermoplastic layer film 13. The seal prevents water, oil and the like from entering between the film layer sealer 10 and layer 2. In FIGURE 1, reference numeral 16 represents an optional chemical primer layer or a corona treatment layer placed between the sealant film layer 10 and a PSA 17 layer.

Chemical and / or physical priming is preferred but is not necessary for the invention. The combination of the layers consisting of the layer 2, the sealing film layer 10, and the priming layer or corona treatment layer 16 is designated as a substrate of a retroreflective, layered material 18. A line (not illustrated) it is preferably placed on the surface of the PSA layer 17 to protect its surface before adhering to a highly monomerically plasticized PVC component 20. FIGURE 2 illustrates another embodiment of the inventive article, respectively. FIGURE 2 illustrates a retroreflector material in cube corner shape 200, comprising a layer 2 as in the embodiment illustrated in FIGURE 1. However, mode 200 comprises a metal layer 3, which serves to reflect light incident in layer 2. No sealing layer is present. FIGURE 2 illustrates a layer of PSA 17 that adheres a plasticized PVC component 20 to the metal layer 3. This embodiment eliminates the need for a sealing film, but requires that the PSA be able to attach a plasticized PVC component to a metal surface.

The layer 2 can be any of the materials in retroreflective, substantially and fully internal or corner corner layers described in U.S. Patent Nos. 3,140,304; 3,648,348; 4,576,850; 4,588,258 4,775,219; 4,801,193; 4,805,984; 4,895,428 4,906,070; 4,938,563; 5,056,892; 5,138,488 5, 175, 030; and 5, 183, 597. More specifically, the layer 2 preferably comprises a large number of precisely formed elements (preferably pyramidal, in the form of cube corners or a series of parallel prisms) defined by the notches that define the elements. The pyramids, in the form of cube corners or prisms reflect substantially and totally the light in a direction opposite to the incident direction. The precisely formed elements define a plurality of bags 11 (FIGURES 1 and 2), filled with air or another fluid. "Substantial and totally internal reflection" pertains to the optical quality of the film, and means that the film has a Test Value T of 5% or less, where the T-Test is described as follows. The optical quality of a retroreflective film can be evaluated with the apparatus including a laser beam (such as a Spectra-Physics Inc. Model 117A) with a spatial filter, an electronic beam expansion mechanism, and a collimator. Two diagrams or irises are placed 18 and 38 cm from the laser, and a support of the annular sample with an opening of 6.35 cm in diameter is placed 84 cm from the laser. Directly behind the sample holder is an integral sphere (with an opening of 3 cm in diameter) and a LABSPHERE ML-400 radiometer. Using the diaphragms or iris, the laser is focused through the opening to obtain a perfect circle of light of approximately 3 mm in diameter on a black surface mounted on the sample holder. A source of intensity measurement of 100% is taken without the sample in place. The TIRF to be tested, then mounted on the sample holder with its flat surface facing the laser and its indentations extend vertically. Unless reported otherwise, the T-Test Values are measured at room temperature. The readings are then made from 12 to 15 different points in the TIRF within an area of 5 cm in diameter, while making sure that no light hits the structure of the sample holder. The readings are averaged and multiplied by 100 to give the transmission in percent which is the Test Value T of the TIRF sample. The Test Value T is a criterion of replication fidelity of the TIRF. The smaller Test Value T percentages indicate better replication fidelity than the larger percentages, and a Test Value T of 5% or less indicates that the film is substantially and completely internally reflective. Layer 2 preferably comprises an acrylic material having excellent durability, such as poly (methyl) methacrylate, polyester (such as polyethylene terephthalate), polyamide, polycarbonate, poly (vinyl chloride), poly (vinylidene chloride), cellulose acetate butyrate, cellulose acetate propionate, poly (ether sulfone), polyurethane, ionomeric resins (such as crosslinked polyethylene / acrylic acid ionomers, metal ion known under the trade designation SURLYN), and the like, and preferably also comprise a UV light absorber. From the aspects of mechanical strength and light reflectivity, layer 2, preferably has a refractive index of about 1.6, which is possible if the layer is made of a polycarbonate resin, an ionomeric resin as described just, or an acrylic resin. The structured layer material or layer 2 can be made as an integral material, for example, by embossing a preformed layer with a described arrangement of cube-corner elements, or by emptying a fluid material in a mold; or these can be made as a product in the form of layers, for example by emptying the elements against a preformed film as taught in US Pat. No. 3,684,348, or by laminating a preformed film on the front face of individual molded elements. Polycarbonates and ionomers are the preferred, integral layer materials. The thickness of the layer 2 preferably ranges from about 50 to about 500 micrometers in terms of the height of the apex of the pyramid or prism to the base of the base portion. If the thickness is less than 50 micrometers, the mechanical strength is not sufficient and a predetermined height is difficult to obtain by the pyramids or prisms, so that the retroreflectivity decreases. If the thickness exceeds 500 micrometers, on the other hand, the total thickness of the retroreflective layer becomes very thick so that handling becomes difficult and the amount of adhesive required is increased. In the present invention, the sealing film layer 10 (FIGURE 1) is involved in the retroreflectivity display by forming an air layer 12 between the sealing film layer 10 and the layer 2. In other words, in order to that layer 2 exhibits retroreflectivity, an air layer may exist below precisely formed elements to produce a change in the refractive index. The sealing film layer 10 is laminated on the structured surface of the layer 2 and the sealing film layer 10 is bonded thereto with heat and / or radiation at a plurality of locations, thereby forming a plurality of bags. of air, sealed. It is understood that "air" is used uniquely as an example and that other fluids may be used, depending on the atmosphere in which the articles of the invention are produced, and provided that the fluid used is significantly different in the refractive index of layer 2 (a difference in refractive indexes of 0.5 is preferred). The processes of US Pat. No. 4,025,159 can be used to effect the bonding of the sealing film layer 3 to the second structured surface of the layer 2. If the water, oil or the like enter between the layer 2 and the layer of Sealing film 10, changes in refractive index and retroreflectivity is decreased. Accordingly, the sealing film layer has the sealing effect for water and the like. The sealing film layer 10 is preferably an article similar to a plastic film comprising a plastic resin, such as polyurethane, polyester, polyvinyl chloride and the like, which may contain a predetermined amount of one or more pigments such such as titanium dioxide (white), silica, red oxide, and the like, added to the resin. Particularly, the blank is suitable for the present invention because the recognition capability of the retroreflective articles of the invention is high.

B. Articles Employing Retrorreflector Layer Material with Spheres FIGURE 3 is a cross-sectional (elongated) view of one embodiment of illustrative article 300 of the invention comprising a retroreflective substrate of internal lenses adhered to a PVC component using an adhesive according to the invention. In this embodiment, the retroreflective layer material substrate comprises a layer of polyvinyl butyral 32 in which a plurality of glass microspheres 34 is embedded. The layer 32 may also comprise other organic layers, such as gliptal, alky, ethylene and / or or propylene acrylic acid copolymers, ethylene methacrylic acid copolymers, ionomers, crosslinked and / or non-crosslinked aliphatic polyurethanes, vinyl, PMMA, and the like. A cover material 38 is illustrated on the printed signal for abrasion resistance, resistance to chemical deterioration, and the like, which would be desired by the users of the inventive articles in prologate weathering (ie, greater than 1 year ), such as license plate, highway signs, street signs and the like. A reflective layer 36, a PSA layer 40, and a plasticized PVC component 42 complete the structure. Preferred internal layer, substrate, retroreflective layer materials include those known under the trade designation SCOTCHLITE, particularly the 3700, 4200 and 5300 series, available from Minnesota Mining and Manufacturing Co. , St. Paul, MN, then in this 3M). Retroreflective, closed lens materials can also be used and illustrative examples are described in U.S. Patent Nos. 2,407,680, 4,664,966 and 4,511,210. Also useful retroreflective substrates are encapsulated lens layer materials such as described in U.S. Patent Nos. 3,190,178; 4,025,159; 4,896,943; 5,064,272 and 5,066,098.

Non-Reflective Items As previously mentioned, non-reflective substrates can be adhered to highly and monomerically plasticized PVC components using the inventive adhesive. Illustrative examples of suitable non-reflective substrates include those polymeric films, mentioned previously that include polyurethane films, polyolefin films, and plasticized vinyl films (such as described in U.S. Patent No. 4,605,592 (Paquette et al.), Or soft metallic films such as aluminum. Other substrates include a tie layer of a hook and loop attachment system such as those known under the trade designation VELCRO and SCOTCHMATE, the latter available from 3M.

Printed Signal It should be noted that the articles of the invention may have signals that can be read by humans and / or machines, such as a desired alpha-numeric signal, bar codes, logos and the like, printed on the exposed surface of the substrate ( that is, that the surface of the substrate has no adhesive bonded thereto), which subsequently can be concealed below the adhesive and the cover film layers, as described in the PCT applications previously incorporated by reference. The printed signal can be printed using wax-based binder substances / dyes or resin-based binder / dye in a thermal mass transfer process, such as described in pending U.S. patent applications of the assignee. Series 08 / 386,279 and 08 / 386,280, both issued on February 9, 1995, and / or the printing using the dry organic pigment olvo processes of the North American patent no. No. 5,085,918 and pending US Patent Serial No. 08 / 335,468, issued November 7, 1994.

Primer Coat The surface of the retroreflective and non-retroreflective substrates that makes contact with the adhesive can be a wide variety of materials. Thus, surface treatments may be necessary to ensure better adhesion to the plasticized PVC component. The particularly preferred thermoplastic resin for forming a sealing film layer are polyester and polyurethane resins. However, the bonding of the polyurethane and polyester films to the adhesive layers is not easy and furthermore, when the processing aids are present on the films, they tend to migrate towards the interface between the adhesive and the film, which causes the weakening of the union. However, when the sealing film layer is printed either physically or chemically, these problems can be overcome effectively. In the present invention, a chemical priming layer or a corona treatment layer is preferably placed between the sealing film layer 3 and the PSA 5 layer. When a chemical priming and / or corona treatment layer is employed, the adhesion of the interlayer between the sealing layer film 3 and the PSA layer 5 can be improved, and in this way the high adhesion of the articles of the invention to a substrate is possible. Suitable chemical primer layers can be selected from urethanes, silicones, epoxy resins, vinyl acetate resins, ethylene imines and the like. The types of urethane and silicone are chemical primers, particularly effective for colored, polyester, sealing film layers. Among the type of silicone, the primer layer having a continuous, gelled network structure of inorganic particles, which is described in Japanese Unexamined Patent Application (Kokai) No. 2-200476, is suitable for the present invention. This is because it has a particularly remarkable affinity for polyester resins and polyolefin resins. Examples of primer materials, chemicals for vinyl films and polyethylene terephthalate include crosslinked acrylic ester / acrylic acid copolymers described in U.S. Patent No. 3,578,622. The thickness of the chemical primer layer is suitably within the range of 10 to 3,000 nanometers (nm). If the thickness is less than 10 nm, the priming effect is minimal and if it exceeds 3,000 nm, on the other hand, peeling of the inter-layer in the primer layer is likely to occur. The corona treatment is a preferred physical primer that can be suitably applied to the unexposed surface of the substrate on which the adhesive of the present invention is then coated. The corona treatment improves the adhesion of the inter-layer between the adhesive and the substrate. Corona treatments of films is a well-known technique, and is generally described in Cramm, RH, and Bibee, DV, The Theory and Practice of Corona Treatment for Improving Adhesion, TAPPI, Vol. 65, No. 8, pp 75 -78 (August 1982), and in the defensive publication, American H 688, published on 3 Octure of 1989.

Pressure Sensitive Adhesives The adhesives useful in the invention are pressure sensitive and preferably have good initial tack (sometimes referred to as "pre-adhesion"), thus improving the easy application of the retroreflective layer material on the components PVC monomerically plasticized. PSAs must have an acceptable performance after plasticizer absorption. During the summer, the temperature on the sides of the PVC-coated tarpaulin of a vehicle pulled by a truck could conceivably reach as high as 54 ° C (130 ° F). This would increase the migration of the plasticizer in the adhesive. PSAs must have acceptable performance after exposure to water or moisture. Under rain conditions, water could be present at the interface between the retroreflector layer material and the PVC coated fabric material. Water would have a greater effect on the performance of the adhesive if it contained more hydrophilic components. In addition, there is preferably no uniform stretching of the retroreflective sheet material during stress conditions, such as when attached to vehicles pulled by a side curtain truck to be opened and closed. Vehicles pulled by a truck would need frequent washing due to the extensive amount of time spent on the road under a wide variety of conditions. The ability of the adhesive to resist delamination during pressure washing is important.

A. Primary Acrylic Acid Esters and Met (Acrylic Acid) Acrylic copolymers useful in the adhesive of the invention, preferably contain from about 50 to about 90 parts per hundred parts by weight of monomer, more preferably about 60 to about 80 parts per hundred parts of the monomer, contained in the copolymer of at least one monomer selected from the group consisting of a first ester of monofunctional acrylate or methacrylate of a tertiary alkyl alcohol, the alkyl group of which comprises from 4 to about 12 atoms of carbon, and mixtures thereof. Such acrylate or methacrylate esters generally have, as homopolymers, vitreous transition temperatures down to about -25 ° C. The higher amounts of this monomer relative to other comonomers gives the PSA with higher tack at low temperature, while lower than about 50 weight percent of this monomer reduces or completely eliminates the pressure sensitivity of the adhesive. Preferred acrylate or methacrylate ester monomers include but are not limited to those selected from the group consisting of n-butyl acrylate (BA), n-butyl methacrylate, isobutyl acrylate, 2-methyl butyl acrylate, 2-ethylhexyl, n-octyl acrylate, isooctyl acrylate (IOA), isooctyl methacrylate, isononyl acrylate, isodecyl acrylate and mixtures thereof.

Particularly preferred acrylates include those selected from the group consisting of isooctyl acrylate, n-butyl acrylate, 2-methyl butyl acrylate, 2-ethylhexyl acrylate, and mixtures thereof.

B. Basic Monomers The copolymerizable, basic monomers are required in the PSAs useful in the invention to increase both the shear strength and shear strength of these adhesives. Polar, basic, copolymerizable, preferred monomers include N, N-dialkyl, moderately basic substituted, and monomers that behave as N, -dialkyl substituted amides. Examples of copolymerizable, moderately basic, useful monomers include N, N-dimethyl acrylamide (NNDMA), N, N-dimethyl methacrylamide, N, N-diethyl acrylamide, N, N-diethyl methacrylamide, N-vinyl pyrrolidone (NVP), N -vinyl caprolactam and the like. The weakly basic copolymerizable monomers, such as N-octyl acrylamide can be used in combination with a higher amount of moderately basic monomer. Strongly basic monomers (monomers having tertiary amine end groups not strictly impeded) such as N-methacrylate, N-dimethylaminoethyl, N, N-dimethyl laminopropyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, and the like, were found to be too basic when used as the basic monomer alone, actually dehydrochlorinating PVC in aging and with this possibly shortening the useful life of the fabric coated with PVC and other PVC components. If strongly basic monomers are used, such as N, N-dimethylaminoethyl methacrylate, it is preferred that these monomers be present in a minor amount and be used in conjunction with a higher amount of a moderately basic monomer. Particularly preferred are polar, moderately basic monomers, alone or in combination with other basic monomers. Preferably, the PSAs useful in the present invention comprise from about 10 to about 25 parts by weight of the copolymerizable, moderately basic monomer. Exemplary mechanical test results are obtained when about 14 to about 20 parts by weight of copolymerizable, moderately basic monomers are present, particularly in conjunction with about 60 parts by weight of isooctyl acrylate and / or sodium acrylate. -butyl as the low Tg monomer, and about 3 to about 6 parts by weight of acrylic acid. The copolymerizable, basic, particularly preferred monomers are represented by the general formula (I). Examples of specific Z groups include, but are not limited to, those selected from the group consisting of C (= 0) N (CH3) 2 and -C (= 0) N (C2H5) 2. The basicity of the nitrogen containing monomers used in the present invention is defined by its substitution. Substituents that increase the electron density in a nitrogen by field or resonance effects in the case of aromatic bases will increase the basicity of nitrogen. The higher the degree of substitution in the nitrogen for linear or branched alkyl groups, the higher the basicity of the monomer. Conversely, substituents that lower the electron density on the nitrogen of a basic copolymerizable monomer, such as a phenyl group, will reduce the basicity of the monomer. Using these general principles, the various copolymerizable, basic, common monomers possess the following ascending order of basicity: Acrylamide <; N-methyl acrylamide < N, N-dimethyl acrylamide < 3- (3-pyridinyl) propyl acrylate < N, N- (dimethyl mino) ethyl acrylate. Moderately basic, copolymerizable, particularly preferred monomers include those selected from the group consisting of N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N, N-diethyl acrylamide, N, N-diethyl methacrylamide, and mixtures thereof.

C. Acidic Monomers Depending on their basicity, the amount of copolymerizable, basic monomer used is from about 10 to about 25 parts per hundred parts of the final copolymer. While a molar excess of the copolymerizable basic monomer is maintained, low levels can be used (typically 0 to about 7 parts by weight, most preferably from about 3 to about 6 parts by weight) of an acidic monomer such as carboxylic acid to increase the cohesive strength of the pressure sensitive adhesive. At higher levels, this acidic, copolymerizable component tends to decrease the tackiness of the pressure sensitive adhesive of the present invention. Acidic, copolymerizable, useful monomers include but are not limited to those selected from the group consisting of carboxylic, ethylenically unsaturated, sulfonic, ethylenically unsaturated, and ethylenically unsaturated phosphoric acids. Examples of such compounds include those selected from the group consisting of acrylic acid (AA), methacrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid and maleic acid, β-carboxyethyl acrylate, sulfoethyl methacrylate and the like, and mixtures thereof.

D. Secondary Acrylate Monomers As previously mentioned, the PSAs useful in the invention preferably exhibit acceptable performance in soaking with water, which can be problematic if the hydrophilic monomers are present. Therefore, from 0 to about 30 weight percent of a hydrophobic monomer having as a homopolymer a Tg greater than -25 ° C, it may be replaced by or partially replace hydrophilic monomers such as acrylic acid. Useful secondary acrylate monomers include isobornyl acrylate (IBA), ethyl acrylate, methyl acrylate, vinyl acetate, and the like.

E. Crosslinking Agents The crosslinking agent is an organic compound that reacts with the other monomers by virtue of having a plurality of ethylenically unsaturated groups. These compounds are referred to herein as multifunctional acrylates. Alternatively, a crosslinking agent is a compound that can react directly with the polymer structure and result in crosslinking, for example, thermal cure with peroxide or cure with UV light of benzophenone. A crosslinking agent is present in an amount of about 0.05 to about 1 weight percent in the pressure sensitive adhesive of the present invention based on the total weight of the monomers employed. The crosslinking agents are selected according to the polymerization method employed. Preferred crosslinking agents for PSAs prepared by means of photopolymerization on cloth are multifunctional acrylates such as 1,6-hexanediol diacrylate (HDDA) as well as those described in U.S. Patent No. 4,379,201 (Heilmann et al.) Such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, 1,2-ethylene glycol diacrylate, and 1,2-dodecanediol diacrylate. Additional, useful crosslinking agents include photorethinkers of the hydrogen abstraction type such as those based on benzophenones, acetophenones, anthraquinones and the like. These crosslinking agents can be copolymerizable or non-copolymerizable. Examples of non-copolymerizable hydrogen abstraction crosslinking agents include benzophenone; crosslinking agents that can be activated with radiation such as those described in U.S. Patent No. 5,407,971 (Everaerts et al.) within the general formula [X-C- - (W) a- (CH 2) m- (Y) a] n-Z wherein W represents -0-, -N-, or -S-, X represents CH3- or phenyl, Y represents a ketone, ester or amide functionality, Z represents a polyfunctional organic segment that does not contain hydrogen atoms that are more Photoabstractible than the hydrogen atoms of a polymer formed using the crosslinking agent; m represents an integer from 0 to 6, a represents 0 or 1, and n represents an integer of 2 or greater; and anthraquinones, while examples of the copolymerizable hydrogen abstraction initiator examples include aromatic, monoethylenically unsaturated ketones, particularly 4-acryloxybenzophenone (ABP), as described in U.S. Patent No. 4,737,559 (Kellen et al.). In addition, photoinitiators of the a-division, copolymerizable type, such as disubstituted acrylamido-functional acetyl aryl ketones (such as those described in the assignee's US patent application Serial No. 08 / 136,576, issued on 13 October 1993. In addition, combinations of multifunctional (meth) acrylates and hydrogen-abstraction-type cross-linkers or copolymerizable, a-division-type photoinitiators can be used: low-intensity UV light, such as "black light" UV rays "is sufficient to induce crosslinking in most cases, however, when crosslinkers of the hydrogen abstraction type are used by themselves, exposure to high intensity UV rays (such as by mercury lamp such as that available from PPG, Aetek and others) is necessary to achieve sufficient crosslinking at high line speeds. cross-linking (not necessarily requiring the addition of cross-linking agents) is by exposure to an electron beam. Other useful crosslinking agents include the substituted triazines, such as those described in U.S. Patent Nos. 4,329,384 and 4,330,590 (Vesley), for example 2,4-bis (trichloroethyl) -6-p-methoxystyrene-5-triazine and chromomethous halomethyl-5-triazines. The crosslinking agents useful in the solution of the polymerized PSAs useful in the invention are those which are copolymerizable by free radicals and which effect crosslinking through exposure to radiation, moisture or heat following the polymerization. Such crosslinkers include the substituted, photoactive triazines mentioned above and photocrosslinkers of the hydrogen abstraction type. The free-radical, copolymerizable, hydrolysable crosslinkers, such as mono-, di- and trialkoxy, monoethylenically unsaturated compounds including but not limited to methacryloxypropyltrimethoxysilane (sold under the trademark "Silane A-174" by Union Carbide Chemicals and Plastics Co. .), vinyl dimethylethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriphenoxysilane, and the like are also useful crosslinking agents. Heat-activated copolymerizable crosslinking agents, including but not limited to N-methylol acrylamide and glycolic acrylamide acid, can also be used to increase the shear stress of the pressure sensitive adhesive composition of the invention. The bisamide crosslinking agents can also be used. The bisamide crosslinking agents are more fully described as compounds within the general formula (I): wherein Rl and R3 are the same or different and are independently selected from the group consisting of H and Cr? H2n + i / wherein n is an integer ranging from 1 to about 5, and R2 is a divalent radical selected from group consisting of benzene (-C6H-), substituted benzene, triazine, and CmH2m where m is an integer ranging from 1 to about 10. An example of a bisamide useful within general formula I is N, N '- bis-1, 2-propylene isophthalamide, having the following structure (general formula II): F. Initiators Suitable free radical, thermal initiators that can be used include, but are not limited to, those selected from the group consisting of azo compounds such as 2,2'-azobis (isobutyronitrile), hydroperoxides such as hydroperoxide -butyl, and peroxides such as benzoyl peroxide and cyclohexanone peroxide. Photoinitiators that are useful in accordance with the present invention include but are not limited to those selected from the group consisting of benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether, substituted benzoin ethers such as anzole methyl ether, substituted acetophenones such as 2,2-diethoxyacetophenone and 2,2-dimethoxy-2-phenyl acetophenone, substituted alpha ketoles such as 2-methyl-2-hydroxy propiophenone, aromatic sulfonyl chlorides such as 2-naphthalene sulfonyl chloride and photoactive oximes such as 1-phenyl-1, l-propanedione-2- (0-ethoxycarbonyl) oxime. For both thermal and radiation induced polymerizations, an initiator is present in an amount of about 0.01 to about 0.5 weight percent based on the total weight of the monomers of the pressure sensitive adhesive compositions present.

G. Glass transition temperature The glass transition temperature (Tg) of the adhesives useful in the present invention is preferably within the range of -10 ° C to about 10 ° C, more preferably of about -5 °. C at about 5 ° C. When the Tg is lower than -10 ° C, the pre-adhesion (stickiness) tends to become excessively high, and when the Tg exceeds 10 ° C, on the contrary, the pre-adhesion tends to become too low. In addition, the values of the Tg in these preferred ranges allow the adhesive to possess good resistance to peel strength of the coating even after the monomeric plasticizer's absorption of the PVC component. The term "glass transition temperature" (Tg) of the adhesives useful in the invention means a measurement value determined through the use of mechanical dynamic analysis (DMA) using a Bohlin VOR rheometer. For each sample of adhesive, the oscillation experiment produced storage (G ') and the least shear relaxation modules (G ") as a function of frequency and temperature.The parallel plates used were 2.54 cm (1 inch) The thickness of the adhesive samples varied from 0.5 to 2 mm For each sample tested, the first set of measurements was taken at 25 ° C. Using liquid nitrogen, measurements were taken at 10 ° C below - 40 ° in 10 ° increments There was approximately a 15 minute interval between measurements at different temperatures to allow the adhesive sample to relax and obtain equilibrium at the hardening temperature At each temperature, the frequency curves varied from 0.63 at 63 rad / sec The normal force remained constant and the power was approximately 20 gm-cm For each sample, G 'and G "were obtained at each temperature. The relation (G "/ G '), a nonunitary parameter, typically represented" tan d ", was plotted against the temperature in a diagram, the maximum point (point where the slope was zero) in the region of transition between the region of glass and the rubber region of curve tan d, if well defined, determined the Tg of the adhesive.

H. Polymerization Methods The adhesives useful in the invention can be polymerized by conventional free radical polymerization methods, either thermally or initiated with radiation including solution and volume polymerization processes. In a solution polymerization method, the acrylate ester component, basic copolymerizable component and acidic polar component together with a suitable inert organic solvent and the free copolymerizable, free radical crosslinker are charged to a four-neck reaction vessel which was equipped with an agitator, a thermometer, a condenser, an addition funnel and a time trial. Then, this monomeric mixture is charged into a reaction vessel, a thermal, free radical initiator solution is added, concentrated to the addition funnel. The reaction vessel and the addition funnel and their contents, as a whole, are then purged with nitrogen to create an inert atmosphere. Once purged, the solution inside the vessel is heated to about 55 ° C, the initiator is added, and the mixture is stirred during the course of the reaction. A conversion of 98 to 99 percent must be obtained in approximately 20 hours. Another polymerization method is a photopolymerization initiated with ultraviolet (UV) radiation, two steps, of a mixture of 100% solid monomers. In the first step, the low viscosity monomers are mixed at the appropriate ratios and a photoinitiator is added to the mixture. The mixture is purged with nitrogen to remove the dissolved oxygen. Exposure to UV light results in a partially polymerized syrup with a moderate viscosity that can be easily coated. In addition, the photoinitiator and crosslinker are added to the syrup. The syrup is then coated (while 02 is excluded) to a desired thickness, usually about 0.5 to 10 mils (approximately 0.01 to 0.25 millimeters). During the coating process, the syrup is further exposed to a bank of UV lights to complete the polymerization and to crosslink the adhesive. An alternative to the two-step method, above, involves the use of an extruder. In this method, a plastic bag is filled with monomers and initiators, with the addition of chain transfer agents to keep the molecular weight sufficiently low after the polymerization so that the polymer can be extruded. The filled bag is exposed to UV light, which produces the polymerized composition within the bag. The bag and the contents are then fed to the extruder and the resulting molten composition is fused, hot coated onto a protective coating, after which, it is then exposed again to UV light or an electron beam to crosslink the adhesive, to producing a composition comprising a high molecular weight PSA having a small percentage of polymeric material in the plastic of the bag therein, typically 3 weight percent or less. Reactive extrusion, such as the continuous free radical polymerization methods described in U.S. Patent Nos. 4,619,979 and 4,843,134 (both by Kotnoour et al.), Can be used to prepare the PSAs useful in the invention. Reactive extrusion is a solvent-free technology where polymerization is initiated by thermal means as opposed to UV light radiation. The monomers together with the initiator are fed to an extruder. The temperature together with the extruder is varied to control the polymerization. The chain transfer agents are added to control molecular weight and prevent gel formation. The adhesive obtained at the end of the extruder is hot molten coated and cured by either UV light or electron beam in order to improve its cohesive strength.

I. Optional Adhesive Solvents and Ingredients Inert organic solvent, suitable, if required, can be any organic liquid that is essentially inert to the reactants and the product, and otherwise will not adversely affect the reaction. Such solvents include ethyl acetate, acetone, methyl ethyl ketones and mixtures thereof. The amount of solvent is generally about 30-80% by weight based on the total weight of the reagents (monomer, crosslinker, initiator) and solvent. Other useful materials that can be mixed in the pressure sensitive adhesive layer, but are not limited to those selected from the group consisting of fillers, pigments, woven and non-woven fabrics, antioxidants, stabilizers, flame retardants and agents that adjust the viscosity.

PVC components There are many types of PVC component materials, monomerically plasticized, including: PVC coated fabric; vinyl films containing as much as 25 to 100 parts of monomeric plasticizer (usually dioctyl phthalate) to 100 parts of vinyl resin; and papers covered with vinyl and cotton fabrics. Other substrates include substrates coated with PVC such as those mentioned in Japanese published Kokai Nos. 5-263055, 5-140523 and 5-105857, incorporated herein by reference. Publication x055 discloses mild vinyl chloride resins containing a stabilizing agent of the metal type, while publication x523 discloses mild vinyl chloride resins containing an epoxy radical. Publication y578 describes plasticized PVC, wherein the plasticizer is one or more of those listed above. The primary component of the fabric coated with monomerically plasticized PVC is the course of polyvinyl chloride. Some fabrics coated with PVC have an acrylate or methacrylate copolymer added to PVC. Fabrics coated with PVC mainly differ in the type and amount of plasticizer added to polyvinyl chloride. These can also differ in their weight; the PVC-coated fabric, more common is a version of 610 grams per square meter or "gsm" (18 ounces per square yard), with the base fabric (usually knitted nylon, polyester, or weft inserted fabric) in general weighing from about 170 to about 340 gsm (from about 5 to about 10 ounces per square yard), more typically from about 170 to about 240 gsm (about 5 ounces per square yard to about 7 ounces per square yard). The heavier base fabrics are used in the liner fabrics of heavier-class trucks, which can weigh up to approximately 850 gms (25 ounces per square yard). Smaller weight fabrics in the range of about 30 to about 475 gsm (1 ounce to 14 ounces per square yard) are also within the invention and are used in applications where weight is important and other physical properties, such as strength to abrasion, they are not important. As previously stated, both the truck covers and cover fabrics are within the invention, including the mesh-type truck covers, which are light in weight, generally about 170 to about 340 gsm (about 5 to about 10 ounces) per square yard). One study identified that the PVC-coated tarpaulins known under the trade designation DURASKIN, style No. B156035, available from Verseidag-Indutex GmbH, Krefeld, Germany, have a high percentage of monomeric plasticizer. An analysis of GC and IR of this fabric coated with blue PVC revealed that the PVC coating contained approximately 40 weight percent of the monomeric plasticizer. It is speculated that highly and monomerically plasticized PVC component materials may contain one or more of the following monomeric plasmids: phthalic acid derivatives such as dimethyl phthalate, dibutyl phthalate, diethyl phthalate, diheptyl phthalate, phthalate di-2-ethylhexyl, diisooctyl phthalate, di n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, diisobutyl phthalate, dibenzyl phthalate, phthalate of butylbenzyl, dicyclohexyl phthalate, dimethoxyethyl phthalate, dibutoxyethyl phthalate, dimethylcyclohexyl phthalate, octyldecyl phthalate, octylbenzyl phthalate, n-hexyl-n-decyl phthalate, n-octyl n-decyl phthalate; isomeric phthalic series such as dimethyl isophthalate, dioctyl isophthalate, di-2-ethylhexyl terephthalate; tetrahydrophthalic acid derivatives such as di-2-ethylhexyl tetrahydrophthalate, di n-octyl tetrahydrophthalate; phosphoric acid derivatives such as tricresyl phosphate, trioctyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, chrysilidiphenyl phosphate, trichloroethyl phosphate, diphenyl phosphate bisphenol A, dixilenyl phosphate bisphenol A; adipic acid derivatives such as dimethyl adipate, dibutyl adipate, diisodecyl adipate, diisobutyl adipate, diisononyl adipate, di-2-ethylhexyl adipate, n-octyl adipate, didecyl adipate, n-octyl adipate n- decyl, n-heptyl n-nonyl adipate, benzyloctyl adipate, dibutyl diglycol adipate; sebacic acid derivatives such as di-n-butyl sebacate, di-n-octyl sebacate, diisooctyl sebacate, di-2-ethylhexyl sebacate, butylbenzyl sebacate; azaleic acid derivatives such as di-2-ethylhexyl azelate, di-hexyl azelate, dimethyl azelate, dibenzyl azelate, dibutoxyethyl azelate, diisooctyl azelate; citric acid derivatives such as triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, acetyl trioctyl citrate; epoxy derivatives such as epoxidized soybean oil; polyesters such as polypropylene adipate, polypropylene sebacate; chlorinated materials such as chlorinated paraffin and chlorinated fatty acid ester; glycolic acid derivatives such as methyl phthalyl ethylglycolate, ethyl phthalyl ethylglycolate and butylphthalyl butylglycolate; trimellitic acid derivatives such as tri-2-ethylhexyl trimellitate and tri-octyl n-decyl trimellitate; ricinoleic acid derivatives such as methylacetyl ricinolate and butylacetyl ricinolate; butyl oleate; petroleum resin mineral oils such as paraffin series process oils, aromatic series process oils, specialized process oil, ethylene and α-olefin oligomer, paraffin wax, fluid paraffin, white oil, petrolatum, acid sulphonic petroleum, petroleum sulfonate, petroleum bitumen and petroleum resin; vegetable oils such as castor oil, cottonseed oil, soybean oil, coconut oil, peanut oil, Japanese wax turpentine resin, pine oil, dipentene, softener pine tar, liquid resin, liquid resin purified; aliphatic acid and salts of aliphatic acid such as ricinoleic acid, phalmic acid, barium stearate, calcium stearate, magnesium stearate and zinc stearate. Among these compounds, one or more can be used.

These plasticizers are generally used in percentages by weight ranging from about 10 to 50 weight percent of the total weight of the PVC coated fabric. It is speculated that the retroreflective layered material can be effectively adhered to the different tarpaulin materials with plasticized PVC using the adhesives of the invention, such as polyvinylidene chloride, polyvinyl acetate, polystyrene, PMMA, polyacetal, polycarbonate, polyamide, acetylcellulose, fluoroplastic, car paints and the like.

Examples and Test Methods The invention will be described more specifically with reference to the following non-limiting examples and test methods. All parts, percentages, and ratios are by weight unless otherwise specified.

Abbreviations and Commercial Names EA ethyl acrylate EHA 2-ethylhexyl acrylate CA 2 an acrylic solvent based on the adhesive known under the trade designation AEROET 1845, by Ashlar.d Chemical Co., Columbus, OH.

CA 3 an adhesive comprising 93/7 IOA / AA crosslinked with 15 N, N'-bis-l, 2- propylene-phosphtaamide CA4 a 65% adhesive blend of an acrylic latex (80/16/4 EA / BA / AA) and 35% of a urethane latex known under the trade designation BAYBOND 402a thickened with a thickener known under the trade designation QR0708, from Rohm and Haas, as generally described in Examples 1-8 of U.S. Patent 5 No. 5,229,207.

CA5 an acrylic transfer adhesive known under the trade designation 9465, available from 3M, comprising IOA / NVP / AA with diisononyl phthalate plasticizer (DINP), as described in the patent North American No. 4, 985, 488.

IBA isobornyl acrylate KB-1 benzyldimethylacetal, available from Sartomer under the trade designation ESCACURE KB-1 AA acrylic acid BA n-butyl acrylate IOA isooctyl acrylate HDDA 1, 6-hexanediol diacrylate hr hour mm. minutes 10 NNDMA N, N-dimethyl acrylamide R.T room temperature (approximately 20-25 ° C) PVC / CF the fabric coated with PVC known under the trade designation DURASKIN, style no. B 156035 20 ABP 4-c iloxybenzophenone ANT anthraquinone CPIA a functional disubstituted acetyl aryl ketone of acrylamide Test Methods Static Cutting Stress Test This test is conducted in accordance with PSTC-7, a procedure specified in "The methods for Pressure-Sensitive Tapes," 8th edition, available from the Presure-Sensitive Tape Council, Glenview, IL., E.U.A. A strip of 12.7 mm X 10 cm of the adhesive to be tested was applied to a sealing film. This was placed on a test panel of the fabric coated with PVC, vertical so that 12.7 mm X 25.4 mm of adhesive is in contact. A manual laminator is used to establish good contact between the adhesive, the sealing film and the test panel of the PVC coated fabric. These samples were conditioned at a constant temperature (R.T.) and a room with relative humidity (approximately 50%) (CTRH) for 24 hours. In this stage, a 1 kg load was attached to a free end of the sealing film and the failure time was observed. The samples that failed were examined by the failure mode. The test is typically used to determine the cohesive strength of the adhesive under shear at room temperature. However, if the adhesion to the substrate or backing is poor or the adhesive is over / crosslinked, the failure is adhesive in nature. If no failure has occurred in 10,000 minutes, the test was discontinued. In addition, the samples were thermally conditioned at 70 ° C (158 ° F) for 1 week and were tested for shear stress performance at room temperature using the same procedure.

Pressure Washing Test This test was in accordance with a General Motors Standard No. 9531P, March 1989, to test the ability of a layered material for visibility to withstand a car wash spray with high pressure. A strip of 25.4 mm X 50.8 mm of the adhesive was laminated to the sealing film of a retroreflective material in cube equine form and this was applied to a test sample of fabric coated with PVC. A manual laminator was used to establish good contact between the adhesive and the fabric coated with PVC. The samples were conditioned at a constant temperature and a quarter with relative humidity (approximately 50%) (CTRH) for 24 hours. Half of the samples were placed in an oven during thermal conditioning at 70 ° C (158 ° F) for 1 week and the other half in a bath with distilled water at R.T. for 10 days. In the removal, the samples were placed in a fixation such that the bottom of the layered material was 212 mm away from an R.T. or spray nozzle with cooler water and the top sloped at a 45 ° angle away from the spray with water. The spray with water was directed to the base of the material in layers for 15 seconds at a pressure of about 8500 kPa. At the end of the test, the bottom of the layered material was evaluated by lifting away from the PVC. If the survey was less than 1 mm, it was assigned a classification step. The article was judged to have failed the pressure wash test if the layered material was raised more than 1 mm uniformly.

T-detachment test of the coating A strip of 25.4 mm X 152.4 mm of adhesive was laminated to the sealing film of a retroreflector cube corner layer material and this was applied as a partial coating to a fabric coated with PVC of similar dimension such that a portion of end of the fabric coated with PVC was free of the adhesive. A manual laminator was used to establish good contact between the adhesive, the sealing film and the PVC coated fabric. The samples were conditioned at a constant temperature (R.T.) and a room with relative humidity (50%) (CTRH) for 24 hours. The interposed material of layer-adhesive-fabric material coated with PVC was called composite. The following peeling tests of the coating were performed to test the performance of the adhesive. a) Peeling the coating after residing 24 hours in the CTRH; b) Peeling the coating after thermal conditioning by placing the compound in an oven at 70 ° C (158 ° F) for 1 week; c) Peeling the coating after placing the compound in a bath with distilled water at R.T. for 10 days. After conditioning, the composite was placed in a tension testing machine known under the trade designation SINTECH such that the end of the material layered with the adhesive was clamped in the upper jaw and the end comprised only of PVC coated fabric was clamped in the lower jaw. The jaws were then separated at 30.5 cm / minute and the force required to effect the separation was observed in N / cm (lbf / pg). The thickness of the original adhesive was 0.127 mm.

Examples Examples 1-4 and Comparative Examples C-1 - C-5 EXAMPLE 1 A mixture of 80 parts of IOA, 15 parts of the copolymerizable monomer, moderately basic NNDMA, 5 parts of AA, 0.10 parts of KB-1, was rendered inert and partially cured by ultraviolet (UV) irradiation (black fluorescent lamp, 40 watt that has 90% emissions between 300 and 400 nm and a maximum at 351 nm and that provides a radiation intensity of approximately 1-2 mW / cm2) to produce a syrup that can be revealed at approximately 3,000 centipoises (cPs ). Then, 0.1 part of KB-1 and 0.08 parts of HDDA were added to the syrup with complete mixing. The sample was coated in a thickness of 127 micrometers between two polyester lining siliconized and polymerized under a bank of the same fluorescent UV lamps. The total UV light dose was about 300 mJ / cm2, which produced a pressure sensitive adhesive. The test samples were prepared as explained in the Test Methods. The substrate was a double layer film comprising a 0.64 mm (2.5 mil) polyurethane layer and a 1.0 mm (4 mil) polycarbonate backing layer, with the polyurethane layer facing the adhesive. The results of the tests for Examples 1-4 and Comparative Examples C-1, C-2, C-3, C-4 and C-5 can be found in Table 1.

Example 2 A test sample was made and tested as in Example 1, except that the adhesive used had a ratio of 80 parts of IOA, 18 parts of NNDMA, 2 parts of AA and 0.08 parts of HDDA were used.

Example 3 A test sample was made and tested as in Example 1, except that the adhesive used had a ratio of 80 parts of BA, 18 parts of NNDMA, 2 parts of AA and 0.08 parts of HDDA.

Example 4 A test sample was made and tested as in Example 1, except that the adhesive used had a ratio of 60 parts of IOA, 25 parts of IBA, 15 parts of NNDMA and 0.08 parts of HDDA.

Comparative Example C-1 A test sample was made as in Example 1, except that the adhesive used had a ratio of 65 parts of IOA, 33 parts of IBA and 2 parts of acrylic acid (AA), which was called CA in Table 1.

Comparative Example C-2 For this comparative example, a test sample was made as in Example 1, except that the adhesive used was CA 2.

Comparative Example C-3 For this comparative example, a test sample was made as in Example 1, except that the adhesive used was CA 3.

Comparative Example C-4 For this comparative example, a test sample was made and tested as in Example 1, except that the adhesive used was CA 4.

Comparative Example C-5 For this comparative example, a test sample was made and tested as in Example 1, except that the adhesive used was CA 5.

Table 1 Comp. T-peeling T-peel Tg coating lining (° C) (N / cm) 1 (lbf / pg) 1 IOA / NNDMA / AA / HDDA 12.1, 5.8, 6.9, 3.3, -3 4.9 2.8 IOA / NNDMA / AA / HDDA 9.3, 5.1, 5.3, 2.9, -14 6.1 3.5 3 BA / BBDMA / AA / HDDA 11.9, 5.6, 6.8, 3.2, -13 7.0 4.0 4 IOA / IBA / NNDMA / HDDA 7.4, 5.1, 4.2, 2.9 , 6.5 3.7 CA-1 IOA / IBA / AA / HDDA 7.2, 0.7, 4.1, 0.4, 6.5 3.7 CA-2 AEROSET 1845 10.5, 1.8, 6.0, 1.0, -35 8.6 4.9 CA-3 IOA / AA 4.0, 0.5, 2.3, 0.3, 1.9 1.1 CA-4 65% of latex 3.0, 4.9, 1.7, 2.8, acrylic (80/16/4 0.7 0.4 EA / BA / AA) AND 35% of a urethane latex CA-5 IOA / NVP / AA / DINP 4.7, 3.5, 2.7, 2.0, -4 3.3 1.9 Strength of the lining peel (initial, 7 days in the furnace, 10 days of rowing) or with water) Peel values of the coating less than 3.5 N / cm (2 lbf / pg) were considered unacceptable and values greater than 5.3 N / cm (3 lbf / pg) were preferred. The adhesives CA-3 and CA-4 gave the unacceptable performance in at least two of the three T-peel tests of the coating. The adhesive CA-5 gave the values close to the unacceptable range in both the test of T-peeling of the coating by thermal conditioning and soaking with water. The adhesives CA-1 and CA-2 exhibited high T-peel values of the 10-day water-soaking coating, but performed poorly on the T-peeling test of the coating after thermal conditioning. The adhesive probably absorbed the plasticizer during the thermal conditioning, and as a result, its performance decreased. In addition, the adhesives of Comparative Examples CA-1, CA-2, CA-3, CA-4 and CA-5 all failed in the pressure wash test after thermal conditioning. In contrast, the preferred inventive adhesive of Example 1 exhibited acceptable T-peel coating values in all tests. The initial adhesion was high (12.1 N / cm ["6.9 lbf / pg])." The values dropped after both thermal conditioning and water soaking, but the coating peel values in both of these tests were a significant improvement over the Comparative Examples. pressure wash test after both thermal conditioning and soaking with water.In comparable T, the formulation 60/25/15 IOA / IBA / NNDMA (Example 4) exhibited lower peel values of the initial coating and with thermal conditioning, than the 80/15/5 IOA / NNDMA / AA formulation of Example 1. However, the adhesive of Example 4 exhibited peeling values of the soaking liner with water 10 days not much lower than peels of the lining residing at RT for 24 hours. The absence of AA and the presence of hydrophobic acrylate, IBA, helped the adhesive to maintain its performance after immersion in water. These and all the IOA / NNDMA / AA formulations passed both pressure washing tests, soaking with water and thermal conditioning. In addition, it should be noted that the adhesive of Example 3 exhibited better T-peel results of the coating than the adhesive of Example 2.

Examples 5-9 Example 5 A premix was prepared using 80 parts of IOA, 15 parts of NNDMA, 5 parts of AA, and 0. 04 parts of KB-1. This mixture partially polymerized under a nitrogen-rich atmosphere by exposure to ultraviolet radiation (black 40 watt lamp) to provide a syrup that can be coated that has a viscosity of approximately 3000 cps. Then 0.05 parts of HDDA and 0.16 parts of KB-1 were added to the syrup and this is coated with a knife over a liner that can be freed from paper coated with silicone-treated polyethylene in a thickness of 0.127 mm (5 mils) . The resulting compound was then exposed to ultraviolet radiation having a spectral output of 300-400 mm with a maximum at 351 nm in a nitrogen-rich environment. An intensity of approximately 3 mW / cm2 was used for a sufficient exposure time to result in a total energy of 550 mJ / cm2. The adhesives of Examples 5-9 were tested according to the above test methods and the results are shown in Table 2.

Example 6 A test sample was made and tested as in Example 5, except that 0.075 parts of ABP were added before the partial polymerization step, and 0.04 parts of HDDA were added preferably 0.05 parts to the syrup.

Example 7 A sample was made and tested as in Example 5, except that 0.108 parts of ABP was replaced by the HDDA, an intensity of about 3 mW / cm2 was used for a sufficient exposure time to result in a total energy of 450 rJ / crn2 in a first healing step, and a second curing step was used with high intensity UV light that used a medium pressure mercury vapor lamp for a sufficient time to produce a total energy in the second step of 250 mJ / cm2.

Example 8 A sample was made and tested as in the Example 7, except that 0.09 parts of ANT were replaced by the ABP.

Example 9 A sample was made and tested as in Example 7, except that 0.3 parts of CPIA were replaced by the ABP.

Table 2 Ex. Comp. Amounts T-peeling T-peeling of the coating lining (N / cm) 1 (lbf / pg) 1 IOA / NN/ AA / 80/15/5 / 0.05 / 11.1, 6.3, 6.3, 3.6, HDDA / KB-1 0.2 3.6 3.6 6 IOA / NN/ AA / 80/15/5 / 0.04 / 12.6, 7.4, 7.2, 4.2, HDDA / ABP / KB-1 0.075 / 0.2 7.7 4.4 7 IOA / NN/ AA / 80/15 / 0.108 / 13.3, 7.0, 7.6, 4.0, ABP / KB-1 0.2 8.4 4.8 8 IOA / NN/ AA / 80/15/5 / 0.09 / 13.1, 7.2, 7.5, 4.1, AN. 3-1 0.2 9.3 5.3 9 IOA / NN/ AA / 80/15/5 / 0.3 / 11.9, 8.8, 6.8, 5.0, CPIA / KB-1 0.2 8.1 4.6 Peeling strength of the coating (initial, 7 days in the oven, soak with water for 10 days) All articles of the invention made using the adhesives of Examples 5-9 passed the static shear test and exhibited acceptable T-peel coating values in all tests. The initial adhesion was high for all these examples. The values fell in both thermal conditioning and water soaking but the peel values of the coating in both of these tests were a significant improvement over the Comparative Examples of Table 1. In addition, the adhesives of Examples 5-9 passed the pressure wash tests, individual after thermal conditioning and soaking with water. In summary, the adhesive formulations based on the IOA / NN/ AA and BA / NN/ AA adhesives, the 80/18/2 BA / NN/ AA formulation and the 80/15/5 IOA / NN/ AA adhesive are particularly preferred for use in the inventive articles. In addition, modifications to the adhesives and articles of the invention will be apparent to those skilled in the art. In this way, the appended claims are not limited to their literal wording or to the modalities specifically described.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following claims is claimed as property.

Claims (18)

1. An article comprising: (a) a layer of pressure sensitive adhesive comprising a crosslinked copolymer of 100 parts by weight of monomer of elements (i), (ii), (iii) and optionally (iv), characterized in that the copolymer comprises: (i) about 50 to about 90 parts by weight of at least one monomer selected from the group consisting of a first monofunctional acrylate or methacrylate ester of a non-tertiary alkyl alcohol, and mixtures thereof, the alkyl group of which comprises from about 4 to about 12 carbon atoms, which as a homopolymer has a glass transition temperature of less than -25 ° C; (ii) about 10 to about 25 parts by weight of a moderately basic, copolymerizable monomer selected from the group consisting of substituted N, N-dialkyl amides; (iii) about 0 to about 7 parts by weight of an acidic monomer copolymerizable with the monomers of elements (i) and (ii) where when the acidic monomer is included, the basic, copolymerizable monomer is present in a molar excess; (iv) 0 to approximately 30 parts in The weight of a second monofunctional acrylate or methacrylate ester of a non-tertiary alcohol having as a homopolymer of a glass transition temperature equal to or greater than -25 ° C; and 15 (v) about 0.01 to about 1 weight percent of a crosslinking agent based on the total weight of (i) plus (ii) plus (iii) plus (iv), wherein the relative amounts of the 20 monomers are selected such that the article passes at least three tests selected from the group consisting of a pressure wash test after soaking with water, a wash test with 25 pressure after thermal conditioning, a static shear test (initial), a static shear stress test after thermal conditioning, a T-peel coating test (initial), a T-peel test of the sheath after conditioning thermal, and a T-peeling test of the coating after soaking with water; and (b) a substrate on which the adhesive is coated.

2. The article according to claim 1, further characterized in that a component with highly monomerically plasticized PVC having at least one surface adheres with the pressure sensitive adhesive to the substrate.

3. An article according to claim 2, further characterized in that the substrate is selected from the group consisting of i) a retroreflective, transparent sheet material having substantially a flat surface and a second structured surface, the second structured surface comprised of a plurality of notches defining a plurality of peaks, a polymeric sealing film bonded to the second structured surface at a plurality of locations, the sealing film contacts the adhesive, ii) a metallized retroreflective sheet material having a substantially flat and the second structured surface, the structured surface having a metal layer therein, the adhesive containing the metal layer, iii) the non-incident surface in the light of a retroreflective layered material with spheres, and iv) non-retroreflective substrates selected from the group consisting of polyester films iméricas and soft metallic films.

4. The article according to claim 2, further characterized in that the component with highly and monomerically plasticized PVC is a fabric coated with highly and monomerically plasticized PVC.

5. The article according to claim 4, further characterized in that the component with PVC comprises from 10 to about 50 weight percent of monomeric plasticizer.

6. The article according to claim 1, further characterized in that the substituted N, N-dialkyl amide is selected from N-vinyl pyrrolidone, N-vinyl caprolactam and monomers within the general formula (I): CH2 = C-Z (I) wherein: R is selected from the group consisting of -H and -CH3; Z is -C (= 0) NR1R2; R1 and R2 independently are selected from the group consisting of alkyl groups having from 1 to 10 carbon atoms.

7. The article according to claim 1, further characterized in that the first monofunctional acrylate ester monomer is selected from the group consisting of n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, 2-methyryl acrylate, acrylate. of 2-ethylhexyl, n-octyl acrylate, isooctyl acrylate, isooctyl methacrylate, isononyl acrylate, isodecyl acrylate and mixtures thereof.

8. The article according to claim 1, further characterized by at least one of the following: a) the moderately basic, copolymerizable monomer about 14 to about 20 parts by weight; or b) the acidic monomer is present in about 3 to about 6 parts by weight; or c) the second monofunctional acrylate ester is present in about 1 to about 30 parts by weight.

9. The article according to claim 8, further characterized in that the moderately basic, copolymerizable monomer is selected from the group consisting of N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N, N-diethyl acrylamide, N, N- diethyl methacrylamide and mixtures thereof.

10. The article according to claim 1, further characterized in that the acidic monomer is selected from the group consisting of ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphoric acids, and mixtures thereof.

11. The article according to claim 10, further characterized in that the acidic monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid, maleic acid, β-carboxyethyl acrylate, methacrylate of sulfoethyl, and mixtures thereof.

12. The article according to claim 1, further characterized in that the crosslinking agent is selected from the group consisting of multifunctional acrylates, substituted triazines, monoethylenically unsaturated silanes, hydrogen abstraction compounds, photoinitiators of the a-separation type, copolymerizable, bisamide and copolymerizable crosslinking agents, activated by heat.

13. A method for joining a component with highly monomerically plasticized PVC to a substrate, characterized in that the method comprises the steps of: (a) formulating a pressure sensitive adhesive composition comprising a crosslinked copolymer of 100 parts by weight of monomer of the elements (i), (ii), (iii) and optionally (iv) wherein the copolymer comprises: (i) about 50 to about 90 parts by weight of at least one monomer selected from the group consisting of a first ester of monofunctional acrylate or methacrylate of a non-tertiary alkyl alcohol, and mixtures thereof, the alkyl group of which comprises from about 4 to about 12 carbon atoms, which as a homopolymer 5 has a glass transition temperature of less than -25 ° C; (ii) about 10 to about 25 parts by weight of a moderately basic monomer, 10 copolymerizable selected from the group consisting of substituted N, N-dialkyl amides; (iii) about 0 to about 7 parts by weight of a 15 acidic monomer copolymerizable with the monomers of elements (i) and (ii) wherein when the acidic monomer is included, the basic, copolymerizable monomer is present in an excess 20 molar; (iv) 0 to about 30 parts by weight of a second monofunctional acrylate or methacrylate ester of a non-tertiary alcohol having as a homopolymer of a vitreous transition temperature equal to or greater than -25 ° C; and (v) about 0.01 to about 1 weight percent of a crosslinking agent based on the total weight of (i) plus (ii) plus (iii) plus (iv), (b) applying the adhesive composition either to a component with highly and monomically plasticized PVC, a surface of a substrate, or both; and (c) joining the substrate with the component with PVC, the adhesive composition placed between the component with PVC and the material forming the surface of the substrate.

14. The method according to claim 13, further characterized in that the substrate is selected from the group consisting of i) a transparent retroreflective layer material having a substantially planar surface and a second structured surface, the second structured surface comprised of a plurality of notches defining a plurality of peaks, a polymeric sealing film bonded to the second structured surface at a plurality of locations, the sealing film containing the adhesive, ii) a metallized retroreflective layered material having a substantially planar surface and second structured surface, the structured surface having a metal layer therein, the adhesive containing the metal layer, iii) the non-incident surface in the light of a retroreflective layered material with spheres, and iv) non-retroreflective substrates selected from the group consisting of polymeric films and soft metallic films.

15. The method according to claim 13, further characterized in that the acidic monomer is present in about 3 to about 6 parts by weight, and the moderately basic monomer is present in about 14 to about 20 parts by weight.

16. The method according to claim 13, further characterized in that the moderately basic monomer is selected from the group consisting of N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N, N-diethyl acrylamide, N, N-diethyl methacrylamide. and mixtures thereof.

17. The method according to claim 13, further characterized in that after step (b) and before step (c) the adhesive is exposed to conditions sufficient to crosslink the adhesive.

18. The method according to claim 22, characterized in that the conditions comprise the step of exposing the adhesive to an electron beam. SUMMARY OF THE INVENTION The present invention provides articles comprising a substrate, preferably a retroreflective layered material, having a coating of a pressure sensitive adhesive composition, and in addition to articles wherein the adhesive adheres the substrate to a component with highly PVC monomerically and monomerically plasticized, preferably a fabric coated with PVC. The adhesive comprises a crosslinked copolymer of a first monofunctional acrylate ester of a non-tertiary alcohol having a homopolymer, a vitreous transition temperature of less than -25 ° C, a nitrogen containing moderately basic monomer therewith selected from the group of consists of substituted N, N-dialkyl amides, an optional copolymerizable acidic monomer, a second monofunctional acrylate ester, optionally of a non-tertiary alcohol having as a homopolymer, a glass transition temperature of -25 ° C or greater, and a crosslinking agent. The invention also relates to a method for bonding a component with highly monomerically plasticized PVC to a substrate, preferably a retroreflective sheet material, using the adhesive.