CN1189867A - Wide range vertical retroreflective delineator and method for making it - Google Patents
Wide range vertical retroreflective delineator and method for making it Download PDFInfo
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- CN1189867A CN1189867A CN96195159A CN96195159A CN1189867A CN 1189867 A CN1189867 A CN 1189867A CN 96195159 A CN96195159 A CN 96195159A CN 96195159 A CN96195159 A CN 96195159A CN 1189867 A CN1189867 A CN 1189867A
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Abstract
Retroreflective article (80) that provides effective retroreflective high consistency at very high entrance angles as well as low entrance angles is disclosed.
Description
FIELD OF THE INVENTION
The present invention relates in big angle of incidence and little angle of incidence and the manufacture method that under wet condition, has the counter-reflective products and this goods of high retrodirective reflection brightness.Described goods are well suited for as road surface identification, or as the vertical obstruction or the sign of wall.
The background of invention
Road surface identification (as be positioned on center line of road or the sideline sign) is important, so that provide visible guiding to automobile driver.As traffic control sign, the road surface identification material has various uses, as the line of short distance track, stop line with at the zebra crossing road surface identification of intersection.Road surface identification commonly used is bonding position that requires on the ground and the adhesive-backed adhesive tape on the length; The surface of this adhesive tape has selected color, and it has the retrodirective reflection characteristic usually.
At present, many flat road surface identifications are based on the optics system of exposing lens, and it comprises being partially submerged into contains granules of pigments (as titanium dioxide (TiO
2) or plumbous chromate (PbCrO
4)) adhesive layer in transparent beads as reflecting element.In use, light is injected microballoon and is refracted by the headlight of vehicle and falls on the reflective pigments particle.The roughly reflection of the direction along original travel path of incident light along vehicle of the part of described light is so that driver's observation.These microballoons depend in part on the low refractive index of maintenance in the air interface of microballoon exposed portions serve to the amount of refraction and the aggregate amount of light.In the rainy day, microballoon is made the rainwater institute of anaclasis decline moistening, thereby it is bigger that the retrodirective reflection performance is descended.
A kind of solution of described problem is the road surface identification of projection, and reflective elements is vertical arrangement a little in this sign.United States Patent (USP) 4,388, the road surface identification that 359 (Ethen etc.), 4,988,555 (Hedblom) and 4,988,541 (Hedblem) disclose has projection, and the reflective elements that exposes lens places the side of this projection.
The also known retroreflective structure of in road surface identification, using encapsulated-lens.These structures are commonly used for guiding point, and these guiding points can be strengthened its effect with continuous paint or adhesive tape sign.For example referring to United States Patent (USP) 5,277,513 (Flanagan etc.) and 5,340,231 (Steere etc.).As a kind of method of improving wet retroreflectiveness, made the encapsulated-lens retroreflective sheeting that has smooth coverlay (being also referred to as emulsion sheet sometimes, surface patch, skin covering of the surface etc.), for example, can be referring to the United States Patent (USP) 4 that discloses the encapsulated lens counter-reflective products, 025,159 (Mcgrath), and disclose the United States Patent (USP) 4 that embeds lens type of retroreflective article, 505,967 (Bailey) and 4,664,966 (Bailey etc.).
United States Patent (USP) 4,145,112 (Crone) have disclosed a kind of goods, comprise bottom retrodirective reflection layer and light guide layer, described light guide layer has the transparent projection of a series of weak points that extend longitudinally, and each projection has upwardly extending leading flank and trailing flank (by the light source definition of wanting retrodirective reflection).Leading flank is set, makes it to intersect (promptly relative vertical), thereby they see through the incident light of most of motor vehicle from approaching but not reflect it with the path of the big angle of incidence light of expecting.Trailing flank is set, and the light that makes it leading flank is seen through makes the light of reflective elements retrodirective reflection pass its light source direction of leading flank reflected back along the path reflection in the predetermined angular range of reflective elements energy retrodirective reflection simultaneously.Must make the upwardly extending leading flank and the trailing flank foundation of each projection and keep accurate Rankine-Hugoniot relations, so that keep enough retroreflectiveness.In addition, the projection of longitudinal extension can make this tool be not flexible.United States Patent (USP) 4,236,788 (Wckoff) have disclosed a kind of road surface identification bar of correlation type, and wherein two of lateral prism sides are adjusted to and make light from a downward internal reflection in side and refract to the space between in succession the prism from another side and enter in the substrate.With United States Patent (USP) 4,145,112 disclosed goods are the same, and it is crucial keeping prismatic two accurate Rankine-Hugoniot relations between top.
United States Patent (USP) 3,920,346 (Wyckoff) have disclosed a kind of zigzag sign bar, comprise the projection that has curved edge and have the reflective elements of placing and embedding wherein up.It is said that the curved edge of the projection of rise has reduced the loss of incident light up, so that all can make sign bright with the incident light irradiation sign bar of wide angle of incidence.In addition, in projection, embed the reflective elements of placing up and cause the angle of light of motor vehicle of approaching narrower, make more effectively retrodirective reflection of goods.
United States Patent (USP) 4,072,403 (Eigenmann) have disclosed a kind of retrodirective reflection assembly, and it need to be specially adapted to the situation of retrodirective reflection under the situation of raining.The assembly of this Patent publish comprises a transparent bead, have one deck individual layer microballoon at the suitable position of this bead, and the reflecting layer places the back side of microballoon.This retrodirective reflection assembly that is sometimes referred to as " little sphere/microsphere retrodirective reflection assembly " is placed in the upper surface of road surface identification, the retroreflectiveness of the light that can be improved under the situation of big angle of incidence.United States Patent (USP) 5,268,789 (Bradshaw) have been reported improved little sphere/microsphere retrodirective reflection assembly and have been made the improved method of this assembly.
European patent 385746 B1 (Kobayashi etc.) have reported a kind of road surface identification, comprise that one deck embeds the big glass microsphere on the retrodirective reflection embedding lens-type substrate surface.It is said that this retrodirective reflection road surface identification is specially adapted to the condition of raining, because described big glass microsphere partly is exposed in the air.But disclosed road surface identification is confined to use microballoon as the light collection material.In addition, only reported the retroreflectiveness that when angle of incidence is 60-80 ° this road surface identification can increase its substrate.Known in this area for the more commonly big angle of incidence of road surface identification purposes (greater than about 85 °).
The road surface identification that uses only has effective retrodirective reflection response in than the ranges of incidence angles narrower range that requires at present.In addition, not desired such effective retro-reflector for the existing road surface identification of some purposes.For example, existing microballoon is partially submerged into the plane road surface identification that contains in the granules of pigments layer and is easy to be seen in about 80 meters distances.Greater than this apart from the time because the relatively large and limited retrodirective reflection efficient of angle of incidence of incident light, make retrodirective reflection brightness decline., except common low retroreflectiveness, be difficult to especially be seen in big angle of incidence at rainy condition lower plane road surface identification.The road surface identification of projection has better wet reflectivity, because rainwater can flow away from the part of projection.But, meet difficulty from the road surface snow removing regular meeting of the road surface identification that has projection, because being stuck on the projection of projection and from the road surface, snowplow regular meeting removes sign.
Even need exploitation under big angle of incidence, also on continuous line, to show the low profile counter-reflective products of high retrodirective reflection brightness, even the retrodirective reflection brightness that it also can be remained valid under big angle of incidence under wet condition.In this article, term " low profile " is meant that goods are low as to be enough to bear the collision of the snowplow in a winter, and what damage does not take place.In addition, need the exploitation counter-reflective products, it is used for can having on the vertical surface (as guardrail, cattle pen (Jersey barrier)) effective retrodirective reflection response in wide ranges of incidence angles.
The general introduction of invention
The invention provides novel, as to be preferably low profile counter-reflective products, these goods have non-obvious performance combination: (88 ° or bigger of very big angle of incidence, for example observe the angle of pavement marker) under have improved retroreflectiveness, under low angle of incidence, have good retroreflectiveness brightness, and it has stronger reverse this reflectivity than road surface identification commonly used under wetness conditions.The present invention also provides the new method of this counter-reflective products of preparation.
Put it briefly, goods of the present invention comprise an encapsulated-lens retrodirective reflection substrate and a series of refracting elements on described substrate front surface.Described substrate comprises a series of reflective elements under continuous transparent covering layer.The mode that refracting element is placed with respect to the retrodirective reflection substrate can make the light that is incident on described a series of refracting element with big angle of incidence be refracted, and makes it to be transferred to substrate and by the substrate retrodirective reflection.With United States Patent (USP) 4,145, the refracting element difference in 112 and 4,236, the 788 disclosed goods, the leading flank of the refracting element of goods of the present invention and trailing flank need not accurately to arrange to obtain effective retrodirective reflection each other.385746 B1 are different with European patent, and refracting element of the present invention is not limited to microballoon.As a result, can be at an easy rate and prepare counter-reflective products of the present invention cheaply.In this article, the leading flank of refracting element and trailing flank can be round, or have straight relatively profile.Counter-reflective products of the present invention utilizes the refraction on the refracting element front surface to guide to substrate with the light of big angle of incidence incident.As a result, goods of the present invention have wonderful bright retroreflectiveness, and have the wonderful life-span.
Counter-reflective products of the present invention is specially adapted to light with the purposes greater than about 85 ° big angle of incidence (as the road surface identification structure) incident.This purposes comprises road surface identification and the incident light purposes from any direction, as horizontal mark.The illustrative example of this horizontal mark comprises symbol and the mark that often places indication cripple parking on the road surface, parking lot; And place arrow and track sign on the road surface of intersection.
In addition, counter-reflective products of the present invention also can be applicable to vertical surface well, and those surfaces of watching with big angle of incidence particularly are as guardrail, building wall, cattle pen, bridge pier, distance pole, traffic tube (barrels) etc. along the alleyway.Except having improved retrodirective reflection brightness in big angle of incidence, counter-reflective products of the present invention be also advantageous in that they also have high retrodirective reflection brightness in the little angle of incidence (in as 30-40 ° at normal) of observing sign usually.This makes goods of the present invention be applicable to the wall and the obstruction of speedway well, and is used for vehicle with the approaching works of wide angle, and this works requires effective retrodirective reflection brightness.For example, article one road has a vertical obstruction and places on the part on this road substantially in parallelly, and the second road intersects with article one road.If have Rectroreflective sheet of the present invention on the surface of obstruction, then this Rectroreflective sheet can provide effective retrodirective reflection to the vehicle near this obstruction from any road, thereby has increased safety.Counter-reflective products of the present invention can the curved surface mode use, as is wrapped on taper and the barrel-shaped road sign, and it is first-class to be wrapped in crooked guardrail, because goods can have thundering incident angle, thereby forms good retrodirective reflection brightness along whole visible part substantially.
Different with the exposure reflection from lens sheet that retrodirective reflection does not take place under wet condition, can reverse reflection when counter-reflective products of the present invention is humidity.That is to say that when the rainwater diffluence but goods are not dried, dew accumulates on the goods in the morning, or under similar situation, counter-reflective products of the present invention can retrodirective reflection under the situation of raining.In addition, the outstanding surface of the formation of refracting element also helps the flow of articles branch that anhydrates to keep wet retroreflectiveness in the road surface identification purposes.But, even make counter-reflective products also can keep its validity in the relatively low profile of the regional protuberate of using snowplow.
Put it briefly, the inventive method comprises: (1) forms and contains a series of reflective elements and the tectal retrodirective reflection substrate of one deck; (2) bonding or form a series of refracting elements on described covering layer, the mode that refracting element is placed with respect to substrate, can make the light that is incident to these a series of refracting elements be refracted, thereby be transferred to substrate, by the substrate retrodirective reflection, and be refracted element and reflect once more, thereby make this light by described goods retrodirective reflection.
Compare with the manufacture method of the counter-reflective products of retrodirective reflection substrate with the existing light guide layer that contains, the preparation method of counter-reflective products of the present invention is simpler.For for example being disclosed in United States Patent (USP) 4,145, the existing counter-reflective products in 112 and 4,236,788 must carefully be arranged light guide layer.On the contrary, refracting element of the present invention if necessary can be on the retrodirective reflection substrate random placement and have random arrangement.In addition, be inessential owing to keep accurate structure for obtaining retroreflectiveness, the collision and the friction from traffic above-ground that therefore can change the light guide layer that has counter-reflective products now are very little to the influence of refracting element of the present invention.At last, owing to need not to keep accurate geometry, thus can select more soft suitableeer suitable material, thus help road surface identification of the present invention to be trapped in ability on the road surface.The accompanying drawing summary is further described the present invention below with reference to accompanying drawings, in the accompanying drawing:
Fig. 1 is the plan view that light guide layer places the on-chip existing road surface identification of retrodirective reflection;
Fig. 2 is the sectional drawing of Fig. 1 road surface identification;
Fig. 3 is the plan view of the illustrative counter-reflective products of the present invention;
Fig. 4 is the sectional drawing of another illustrative counter-reflective products of the present invention;
Fig. 5 is the sectional drawing of another illustrative refracting element of the present invention;
Fig. 6 is the sectional drawing of the illustrative refracting element of the present invention;
Fig. 7 is the fragmentary cross-sectional view that shows the illustrative counter-reflective products of the present invention of contact angle.
These Utopian and out-of-proportion accompanying drawings are being illustrative rather than definitive thereof property only.
The detailed description of illustrative example of the present invention
Rectroreflective sheet of the present invention has new optics system, and it can increase the retroreflectiveness of substrate in big angle of incidence under the situation of the retroreflectiveness of not obvious all other angle of incidence of obstruction." incident " angle is defined as the angle (there is glossary at the end at this manual) between reference axis and the incident axle.In this article, " big angle of incidence " is meant greater than about 85 ° angle.Because the light of the big angle of incidence of goods energy retrodirective reflection of the present invention, so it can be used for horizontal purposes (as road surface identification).Because sheet of the present invention has good angular properties (angularity) and have good positive retrodirective reflection brightness, so it can be applicable to vertical purposes, as wall and obstruction sign." front " brightness refers to little angle of incidence, usually by 0 ° to about 30-40 ° brightness.
Fig. 1 and 2 is existing counter-reflective products (as United States Patent (USP) 4,145,112 is described), and wherein goods 10 comprise light guide layer 12 and the retrodirective reflection substrate below it 14 and the optional lower floor's adaptation layer 18 that has internal reflection projection 16.Common this goods also are included in the adhesive phase (not shown) of adaptation layer 18 downsides, and described goods are bonded on the surface (as the road surface (not shown)) of requirement by this adhesive phase.As mentioned above, projection 16 utilizes internal reflection to make the light changed course of big angle of incidence inject substrate 14, utilizes internal reflection to make the retrodirective reflection light changed course retroeflection of substrate 14 to light source direction subsequently.Figure middle level 12 usefulness intermediary adhesive layer 13 are bonded on the substrate 14.Substrate 14 is included in a series of cube corners (cube corner) reflective elements 20 and the diaphragm seal 24 on its back side of main layer 22, diaphragm seal 24 forms the essential interface of retrodirective reflection by the main layer 22 of network sealing of the adhesive tape 26 of intersection on cube corner element 20.
I. the general structure of goods of the present invention
A kind of illustrative counter-reflective products of the present invention is shown in Fig. 3.Road surface identification 30 comprises retrodirective reflection substrate 32, has a series of photorefractive element 34 on the upper surface of substrate 32, optional adaptation layer 36 be positioned at substrate 32 below, optional adhesive phase 38 be positioned at adaptation layer 36 below.
Can use dissimilar Rectroreflective sheets as substrate 32.Retrodirective reflection substrate itself generally can not form enough retrodirective reflections down in very big angle of incidence (as 86-89 °).But,, can obtain good retrodirective reflection performance in big angle of incidence and little angle of incidence simultaneously when these substrates are used for composite article of the present invention.
Photorefractive element 34 is bonded on the front surface of retrodirective reflection substrate relatively flat.Owing to place these elements, these refracting elements can be caught the light that is reflected by minute surface in big angle of incidence usually.The light of being caught is refracted element refraction, injects substrate 32, and this light is by 32 retrodirective reflections of substrate, and is refracted once more, so that penetrate back original light source direction.
Counter-reflective products of the present invention can (in as refracting element and/or in one or more unit of substrate) contain colorant at least a portion of these goods.The illustrative example of colorant commonly used comprises white, Huang Hehong, although also can contain other colorant if necessary.
Simultaneously, on the upper surface of counter-reflective products, can apply one deck thin abrasionproof and/or dustproof coating, so that these goods exempt from the wearing and tearing and the build up of dirt of the vehicles.Be preferably, coating is optically transparent, can't reduce the skid resistance of goods of the present invention.
The illustrative counter-reflective products of another the present invention is shown in Fig. 4.Road surface identification 80 comprises refracting element 60, antiskid particles 62, the retrodirective reflection substrate 82 of high angle performance, optional adaptation layer 78.Substrate 82 also comprises the reflective elements 68 that embeds in the transparent polymer matrix 65, reflecting layer 70, adhesive phase 72 and randomly contain the covering layer 64 of skin covering of the surface 66.As shown in Figure 4, refracting element 60 is hemispheric substantially.Skin covering of the surface 66 can be used for increasing the bonding force between refracting element 60 and the substrate 82.
II. retrodirective reflection substrate
Can use various types of retrodirective reflection substrates in the present invention.The illustrative example that can be used for retrodirective reflection substrate of the present invention includes, but are not limited to embed lens retroreflective sheeting and sealing lens retroreflective sheeting (promptly can be microspheric and cube corner type).Equally, carry out minute surface coating or metallized cube of gusset plate on the surface of cube corner element and also can be used as substrate.The metallization that is known in the art cube corner sheeting can increase the angle of incidence of this sheet.
Be used for retrodirective reflection substrate of the present invention and preferably have good angular properties, that is to say, in relatively large (80 ° or bigger) angle of incidence, the retroreflectiveness of substrate is still quite big.In the road surface identification purposes, even the road traffic instrument ground substrate and caused under the situation of repeated collision and shear stress, all components layer of reverse reflective substrate preferably still is bonded together under various weather conditions.
Illustrative sealing reflection from lens sheet comprises the microballoon base Rectroreflective sheet that contains the single-layer and transparent microballoon, and described microballoon is partially submerged into adhesive layer, and part (being embedded part) has the reflecting layer in the back.Place the covering layer of microballoon front to form air interface.Perhaps, also can use the cube corner type reflector plate of the individual layer cube corner retroreflective element of protecting by sealant with air interface.The cube corner section bar material that also can use cube corner element to be covered by specular reflective metal layers.In cube corner type reflector plate, covering layer can be the integral part of cube corner structure, perhaps can be independent film.United States Patent (USP) 4,025,159 (McGrath) have disclosed some and have been applicable to microspheric of the present invention and cube corner type sealing lens retroreflective sheeting.
Illustrative embedding reflection from lens sheet comprises microballoon base Rectroreflective sheet, and it contains (1) front surface and rear surface and embeds single-layer and transparent microballoon in the transparent medium and (2) and place reflecting layer behind the microballoon rear surface with selected distance.In this article, term " covering layer " is meant any layer in the microballoon front.United States Patent (USP) 4,505,967 (Bailey) have disclosed and have been specially adapted to the present invention and are to embed lens retroreflective sheeting preferably.
Be used for the covering layer that Rectroreflective sheet of the present invention is included in the substantially flat on its front.Substrate component layers below the protection of described covering layer, this covering layer can be individual layer or multilayer.Covering layer is polymer normally, but also can be other light transmissive material if necessary.These materials are selected to make the various characteristics optimization of substrate.
When as road surface identification, embed lens retroreflective sheeting and be better than sealing lens retroreflective sheeting usually.Owing to unlike sealing reflection from lens sheet, contain internal voids, believe that the solid construction that embeds the reflection from lens sheet has the longer life-span under the transportation condition being used for.Long-life and flexible embedding lens retroreflective sheeting can commercially availablely be buied.In example, compare them and can have bright retroreflectiveness in bigger angle of incidence with the system of many sealing lens.In addition, the reflecting layer in many embedding reflection from lens sheets is aluminium and uses the aluminium adaptation layer usually in the road surface identification material.The etching problem that this identical materials different metal capable of reducing using may run into.
Microballoon base encapsulated-lens optics system utilize microballoon to the bending of light and focussing force with anaclasis to reflector parts, light is reflected, subsequently its original direction of bounce back.The optimum position of specific refraction and specular reflector depend on covering layer, microballoon and microballoon above the microballoon and the wall between the reflector parts (if any words) relative index of refraction.For example, if use the covering layer and the material spacer layer of refractive index about 1.5, refractive index is that 2.25 microballoon can be located at identity distance thereafter light focusing from 0.44 times that is about its radius.The thickness of wall preferably approximates this distance, so as with light focusing on specular reflector.Any deviation of this accurate optical relation all can cause the loss of the retroreflectiveness of substrate.Therefore, covering layer preferably keeps the relation of tightly adhering to the microballoon layer, and microballoon preferably stably is arranged in matrix, and light carry out retrodirective reflection must process all layers all preferably transparent and do not have a distortion.In addition, specular reflector (being generally the aluminium of steam deposition) preferably is held in layer, flawless and corrosion continuous substantially, that do not have distortion.The interface of wall-specular layer preferably keeps smooth and corrugationless.The minor variations of these optical relations all can make the retroreflectiveness of substrate descend, thereby involves any goods of being made by this substrate.Although minimum variation can not cause the luminance loss that is harmful to, slight variation can influence these accurate relations consumingly.If any Rectroreflective sheet made from these accurate optical relations can bear the influence that the repeated collision of the vehicles and shear stress and sunlight, rainwater, road grease, road sand grains, road salt, Vehicular exhaust are combined, and will be wonderful.
When light is injected the Rectroreflective sheet that embeds lens with big angle of incidence and by microballoon, with different with the situation that light was produced of more vertical mode incident with little angle of incidence, light can be focused on the side of microballoon but not the back side.Therefore, keeping accurately between microballoon and reflecting layer is important at interval.Those of skill in the art's understanding in this area, can pass through the partly thickness of control interval coating of manufacture method.When wall becomes hemispherical ground suitable with microballoon, promptly concentric with the back side of microballoon, can obtain optimal spacing for various angle of incidence.United States Patent (USP) 4,505,967 (Bailey) have disclosed and have been applicable to embedding lens retroreflective sheeting of the present invention, and describe the relation between the retrodirective reflection response of the arrangement of wall and Rectroreflective sheet in detail.An illustrative example that is applicable to commercially available Rectroreflective sheet of the present invention is 3M SCOTCHLITE BrandReflective License Plate Sheeting No.3750.
Be positioned at light transmitting surface film on the cover surface of retrodirective reflection substrate (if any words) life-span be important because in some applications road surface identification is placed on the busy traffic route.Skin covering of the surface preferably continuous substantially and belong to same class chemical substance with refracting element so that element and covering layer can be fused together form permanent bonding.Described element perhaps, can use other component, as long as can be bonded on the described component well.Skin covering of the surface preferably can the anti-soil thing gathers, transparent, have enough flexible with consistent with road surface, have an alap elastic force, can be with inorganic antiskid particles bonding and in use significantly do not change color.
III. refracting element
According to the present invention, a series of photorefractive element are bonded on the covering layer of retrodirective reflection substrate.In this article, " a series of " are meant many refracting elements, and no matter they are to arrange in order or unordered placement.Described element is normally discontinuous.Fusing together in manufacture process, refracting element is bonded on the covering layer of substrate usually substantially independently of each other except very few elements is superimposed.But, although discontinuous refracting element is preferably, also can use continuous refracting element, as refracting element being linked together with lower floor's sheet material.For example, can make and be included in the projection (being refracting element) that a side has a series of suitable shapings, be the coverlay of the sheet material on plane generally.Can use any suitable method to make this coverlay, as extrude embossing or casting and curing.Coverlay can be fixed on the covering layer of substrate.Refracting element can have essentially identical size and dimension, or is of different sizes and shape.Refracting element can be arranged in an orderly manner or randomly arrange.
The performance that refracting element requires comprises the high grade of transparency and glossiness anti scuffing surface.The transparency of element is important, so that incident light sees through refracting element and minor losses is only arranged, makes most of incident optical energy retrodirective reflection return its light source direction.The surface of refracting element is anti scuffing preferably, makes it to keep glossiness and the light can be by the scratch scattering.Refracting element preferably has the pressing effect of enough hardness with the tolerance vehicles, and in not obviously deliquescing of the temperature that is lower than about 75 ℃ (170).The Xiao Er D hardness that is preferably subelement at least is at least 45.In addition, the collision of the vehicles can not cause the refracting element cracking under the temperature of-40 ℃-75 ℃ (40-170).Refracting element is preferably also bonding well with the retrodirective reflection substrate, and preferably oil resistant, resistant thing, water-fast.Other requirement of refracting element or preferable performance comprise light colour, low cost, low melting point and low melting viscosity.
Being applied to the on-chip refracting element of retrodirective reflection of the present invention can be glass, pottery or polymer.
Be suitable for comprising Merlon, acrylic resin, polyurethane, polyvinyl chloride and polyolefin copolymer, as comprise ethylene-methyl methacrylate (EMAA), ethylene-acrylic acid (EAA), the EMAA of ionomer or polyethylene-acid copolymer of EAA as the illustrative example of the polymeric material of refracting element.Material is an aliphatic urethane preferably because it have good anti-collision, low-temperature flexibility, color, transparency, abrasion resistance and with the tectal bond strength of substrate preferably.
If refracting element directly is formed on the retrodirective reflection substrate and can damages described substrate owing to the high temperature in making, the retrodirective reflection substrate layer can be pressed on the sheet material that is attached with refracting element in advance.Perhaps, select refracting element composition, make them can form and be bonded on the covering layer and can close and require ground to damage described covering layer with low melting glass characteristic.In addition, if necessary, can use non-molten system, form refracting element as liquid monomer composition, solvent evaporates composition, steam hardening composition and the bi-component reactive systems of curable (solidifying) as electron beam or ultraviolet light irradiation.
The horizontal section (that is to say, with parallel plane, road surface identification surface) that should be appreciated that refracting element can have the shape of any requirement, as ellipse, semicircle, Long Circle, rectangle, non-equilateral, equilateral etc.All need on all directions in the example (as the road surface identification of intersection) of best retrodirective reflection brightness at some, the cross section of refracting element better is almost circular.
Usually the major part in each refracting element (for example, at least 75%, better at least 85%, preferably whole substantially) be exposed to tectal above.
Usually the height of refracting element better is about 0.2-6.0mm, preferably about 1-4mm, when the level cross-sectionn is circle its diameter be 1-20mm. simultaneously, the average bottom width that requires refracting element is 2-5 times of average height of refracting element.The refracting element desired shapes is hemispherical or the part of hemisphere.The contact angle of refracting element and substrate is preferably about 45-135 °, is preferably 60-110 °.This shape can make the incident light of big angle of incidence be reflected and enter substrate by leading edge.In this article, " contact angle " is meant by following two angles that line forms, (1) article one line, its end points is in refracting element and substrate contact position, and surperficial tangent at this end points and refracting element, (2) have the second line of same endpoints, it is positioned on the plane identical with described tangent line, and with the substrate surface isoplanar.As shown in Figure 7, refracting element 90 is limited by the first lines A and the second lines B at the contact angle θ of end points P with substrate surface 92.
Another illustrative refracting element shape is a frustum.For example about 1mm height, upper base is the square of about 1mm, going to the bottom is the square of about 4mm, upper base and the center-aligned of going to the bottom, the angle of side and bottom surface (being contact angle) is that 33.5 ° refracting element can be applicable to the present invention well.This refracting element can be refracted into substrate with the incident light of most big angle of incidence.In general, the longitudinal section of at least one side of described cone is a straight line, and the contact angle of itself and substrate is about 30-70 °.
Refracting element can comprise that also sharp-pointed part is used to increase skid resistance.In some cases, this sharp-pointed part can be a polymer.If necessary, this part can form when making refracting element.For example, can extrude the coverlay that on the surface of continuous sheet, has a series of refracting elements, comprise sharp-pointed part on the refracting element.Sharp-pointed part can be the antiskid particles from the refracting element upper process, to replace constituting the projection of refracting element material.Antiskid particles can embed refracting element.Be preferably, the position of sharp-pointed part is as far as possible near the upper surface of refracting element, farthest to bring into play skid resistance.But sharp-pointed part can place the lip-deep any position of refracting element, as long as can increase skid resistance.
At least on one side (being called the front) of the longitudinal section of refracting element (promptly vertical with substrate surface section) should have enough slopes, makes refracting element the incident light of big angle of incidence can be refracted to the retrodirective reflection substrate.But, should avoid having the very low slope refracting element of (being that contact angle is less than 10 °).This low slope can be with light minute surface reflection from the refracting element.Usually, the longitudinal section of refracting element is round.
In some instances, for example as shown in Figure 5, the refracting element longitudinal section has linear edge.Refracting element 50 on substrate 52 has straight front side 54 and straight rear side 56.The light 58 that is incident on the front side 54 is entered substrate 52 by front side 54 refractions, so that carry out retrodirective reflection.With United States Patent (USP) 4,145,112 (Crone) and the described refracting element difference of 4,236,788 (Wyckoff), front side of this refracting element and rear side need not to ask mutually that accurate orientation is to obtain retroreflectiveness.In addition, different with the light induction element with reflection function that these lists of references disclose, the photorefractive element of goods of the present invention can be made by material quite flexible, that rigidity is lower, thereby has obtained very long life of product.The element of described these Patent publish requires the second surface of element directed with first surface, and has the performance that light is reflexed to substrate.On the contrary, refracting element of the present invention relies on (usually on single surface (as front surface)) refraction performance.Thereby need not to arrange first and second surfaces so that second surface can retrodirective reflection, and need not to make second surface to have reflectivity (for example by polishing).It is stricter than the needed performance of refraction usually to reflect needed performance.At last, the disclosed goods of these lists of references do not relate to the substrate of the light of the big angle of incidence incident of employing (as being applicable to of the present invention) energy retrodirective reflection.
Be preferably, the shape of photorefractive element should make to be refracted with the major part in the about 70-90 ° of light that is incident to goods and enter the retrodirective reflection substrate.According to the present invention, with greater than 89 °, the retrodirective reflection brightness when the retrodirective reflection brightness that is incident to the light in the goods of the present invention greater than 85 ° angle of incidence is higher than independent use substrate usually.
Spacing between refracting element can be identical, perhaps arranges described refracting element in random mode.Each element can be placed not according to best mode in need not the purposes of optimal brightness.The characteristic of the random placement of this refracting element can be simplified manufacturing and reduce manufacturing cost.But in the present invention, it is useful placing refracting element in a particular manner equably, because refracting element can specific correlation be placed on the appointed positions, makes each refracting element not cover other element.Refracting element can be caught most of incident light by this way, so that obtain best retrodirective reflection brightness in the geometry of road surface identification.For example, reflective elements can be placed at interval,, and be increased the surface of containing the space of outstanding antiskid particles between vehicle tyre and the refracting element and contact so that cover the part minimum what the angle of incidence direction of expection made adjacent refracting element.Be preferably, the surface area that refracting element occupies preferably less than substrate surface long-pending 50% so that make compliance (as to road, guardrail or other works) maximum of goods of the present invention.Best is that the surface area that refracting element occupies is less than 25%.
Can use protective coating that the goods of the present invention that contain refracting element are protected.This coating has advantage wear-resisting and/or the anti-soil thing.The illustrative example of protective coating includes, but are not limited to ceramic body (ceramer) coating or crosslinked water-based polyurethane coating.
In this article, term " ceramic body " is meant the fluid of the colloidal silica particles that contains the surface modification in the organic liquid that is dispersed in free redical polymerization.The advantage of this coating comprises can bear the performance that outdoor condition has good water-fast branch, fast light photograph and heat; Wear-resisting, resistance to chemical attack and motor vehicle machine oil and carbon black (as the tire carbon black) painted; Optical property (as the transparency) with requirement; Has excellent adhering and good flexible with refracting element.As the first step, earlier ceramic body coating composition precursor is applied on the surface (upper surface and the substrate that preferably include refracting element are not refracted the part that element covers) of counter-reflective products.Coating composition comprises about 20-80 weight % ethylene linkage unsaturated monomer, the cataloid of about 10-50 weight % acrylate functional and about 5-40 weight %N, dibasic acrylamide monomer of N-or N-replacement-N-vinylamide monomers; Wherein said percentage is the percetage by weight of described coating gross weight.Hardening composition subsequently forms and has the ceramic body coating of abrasion resistance, printing opacity.Can use that known method applies the ceramic body composition in many fields of the present invention, comprise that spraying, roller coat, dipping or scraper apply.The undelegated U.S. Patent application 08/444076 of assignee (submit to May 19 nineteen ninety-five, all draws at this to be reference) has disclosed and used the ceramic body coating on road surface identification and Rectroreflective sheet.
The illustrative example that is applicable to crosslinked water-based polyurethane protective coating of the present invention comprise the NEOREZ R-960 board polyurethane resin crosslinked with CX100 board crosslinking agent (all available from Zeneca Resins, Wilmington, Massachusettes).Those of skill in the art in this area will appreciate that, also can use other aqueous based systems and crosslinking agent preparation protective coating.
IV. manufacture method
The inventive method comprises: (1) forms and contains a series of reflecting elements and tectal retrodirective reflection substrate, (2) bonding or form a series of refracting elements on described covering layer, the mode that refracting element is placed with respect to substrate can make the light that is incident to refracting element with big angle of incidence be refracted, transfer to substrate, and by the substrate retrodirective reflection, be refracted the element refraction subsequently once more, so that make described light by described goods retrodirective reflection.
In the concrete manufacture method of making road surface identification, substrate (for example, 3M SCOTCHLITEBrand Reflective License Plate Sheeting No.3750) can be placed on the aluminium adaptation layer.Refracting element is bonded on the covering layer of substrate subsequently.
Can use several different methods that refracting element is bonded on the substrate.For example, when refracting element when being preformed, can be simply with its bonding separately (as by heat and pressure lamination, use adhesive etc.) on the tectal front surface of substrate.Perhaps, can use the method for for example extruding embossing that a series of refracting elements are formed on as projection on the skin of belt surface film, to produce coverlay.This coverlay can be laminated on the covering layer of substrate.
Under some situation (making by thermoplastic resin) as refracting element, can by for example spray, distribution etc. is applied to the resin particle of appropriate size on the tectal front surface, apply enough heats at time enough subsequently and make the resin particle distortion, flow into circle and be bonded on the covering layer.In this case, covering layer and refracting element must form good bonding between the two under heating.Usually, they preferably belong to the thermoplastic polymer with gang.If necessary, covering layer can contain the skin covering of the surface that belongs to same adoption compound with thermoplastic resin particle.
In manufacture method, usually with refracting element attached to the on-chip antiskid particles (as the words of using) that adds simultaneously.Equally, according to the position of needs colorant in goods, can add colorant (as pigment and/or dyestuff) by the appropriate time in manufacture process.
Goods of the present invention be positioned at assembly below the retrodirective reflection substrate, preferably select according to application requirements.For example, lax nonwoven binder (being the saturated lax supatex fabric of polymer that adhesive is arranged) can make the adhesion characteristic that counter-reflective products has enhanced strength and selects.Those of skill in the art in this area can easily select suitable adaptation layer, adhesive phase, enhancement layer etc.
According to the original-shape of (1) process conditions, (2) element, the melting characteristic of (3) polymer and the tectal variation of (4) retrodirective reflection substrate, the net shape of polymer refracting element can be different.According to its original-shape and process conditions subsequently, refracting element can have random shape or consistent relatively shape.
Fig. 6 has described the vertical sectional shape of the three kinds of refracting elements 42,44,46 on the just tectal or front surface 48 of retrodirective reflection substrate of the present invention.Refracting element of the present invention is that glass, pottery or polymer are not spherical, but the part of ball.The part of refracting element 42 on surface 48 approaches complete spheroid.For example, refracting element 42 is the thermoplastic resins that are partially submerged into tectal refracting element of substrate or partial melting.Refracting element 44 is a hemisphere; That is to say that refracting element deeper embeds the covering layer or the more thermoplastic resin of fusion of substrate.Refracting element 46 is more flat relatively; That is to say that it is the thermoplastic that passed through long-time heating.
Be preferably the contact angle that forms between the edge of refracting element and the substrate front surface under the refracting element bottom surface and be about 60-110 °.Can there be the space in substrate with the element of bigger contact angle contact, and dirt may be detained in described space, thereby reduces optical property.Bigger contact angle also can make the bonding firm degree of refracting element and substrate descend.But, the refracting element that contacts with less contact angle with substrate can minute surface reflection incident light but not with its refract to substrate retrodirective reflection subsequently it.In addition, the refracting element with little contact angle has less vertical height, collects performance thereby reduce its light.
Usually the longitudinal section of the refracting element of goods of the present invention better has the profile of refracting element 44, promptly is hemisphere substantially.The shape of refracting element preferably can make the major part of incident light be refracted into substrate.
As the vertical sectional shape meeting build up of dirt and the chip of refracting element 42, thereby reduce retrodirective reflection brightness.And so circular refracting element is easier to fracture from the retrodirective reflection substrate, because the contact area of refracting element and substrate is too little.This refracting element as refracting element 42 is to use relatively short baking oven heat time heating time and/or relatively low oven temperature, makes the thermoplastic element suitably not flow and to flatten and makes.But the counter-reflective products of the present invention that can will have this shape refracting element is used for satisfactorily not bumping (comparing with the road surface identification that was ground by the vehicles) and can be by the vertical purposes of rain-out, as the side of hindrance to traffic.
It is higher that refracting element 46 shows that the thermoplastic element is heated long time and/or heating-up temperature, makes element more straight.Compare with round refracting element, the bonding of this flat element and reflective elements is more firm, but according to the vertically profiling of leading edge, its refraction is less, makes that the retrodirective reflection when big angle of incidence of the goods that form is less.Round element (as refracting element 44) can form higher retrodirective reflection, because light is refracted to a greater degree.Exist a higher outburst area to catch incident light, its scattering or the incident light that reflects from the surface are less usually.
If apply polymer refracting element and heating subsequently in random mode, heating can make some refracting elements flow to together.Although the reflectivity of the refracting element of Xing Chenging is lower than two independent refracting elements thus, common this becomes oval-shaped refracting element and still has tangible reflectivity.If oval-shaped refracting element is laterally placed road traffic, can obtain maximum reflectivity from this element.
V. colorant
Can make and in many ways colorant be added part selected in the counter-reflective products or add in the whole counter-reflective products.In road surface identification was used, the illustrative example of the colorant of requirement comprised white, yellow, redness and blue.As required, colorant can be printing opacity or opaque.
Usually, if colorant is placed light path, it is printing opacity normally, thereby avoids the decline of retrodirective reflection performance.However, it should be understood that opaque colorant to be placed in some cases and can reduce the position of retrodirective reflection brightness, and form the effect of other requirement, as more dazzling overall color or outward appearance.
The colorant of printing opacity can strengthen goods of the present invention by day with the color in night.In road surface identification and other application, the painted sign (identifying as yellow and white) of automobile driver difference is important.A kind of method that obtains the color in night comprises that the material that printing opacity is painted places light path.
In one approach, use painted substrate to obtain color.For example, in Fig. 4, can use the light transmission medium 65 of color (as yellow) with requirement.In sealing lens cube corner type substrate, cube corner itself can be painted.If necessary, another kind of method adopts painted skin covering of the surface.For example, can use yellow, redness or the blue skin covering of the surface of printing opacity to prepare goods of the present invention.Equally, can use painted refracting element.When painted light transmitting surface film and painted printing opacity refracting element use together, can obtain effectively painted counter-reflective products.Perhaps, the dyed layer of printing printing opacity on the covering layer of substrate.On the substrate surface of printing, can apply colourless skin covering of the surface.The advantage of this method is to have hidden dyed layer to increase its life-span.Equally, printing can apply the multilayer color layer that forms pattern, to form symbol or the character that requires.
Opaque colorant is mainly used in the color on daytime that increases goods of the present invention usually, and preferably places light path outer in order to avoid reduce the retrodirective reflection performance.Therefore, by add opaque colorant can be owing to the aluminium reflecting layer color change of the original grizzly substrate color that becomes to require.For example, a kind of method for preparing white goods need use white, opaque part to cover the substrate that has photorefractive element.Although not retrodirective reflection of the part incident light that these are specific, a small amount of whiteness of using this part can increase reflector plate.For example, resin (can be the resin identical with the photorefractive element) bead of white can be applied on the substrate between the photorefractive element and heating, make it fusion and be bonded on the substrate.
Perhaps, but will be applied on the part and substrate of photorefractive element with the part that requires colour coloring, though the retrodirective reflection response is descended to some extent.For example, a kind of method for preparing colored counter-reflective products, comprise the following steps: that (1) formation contains a series of reflective elements and tectal retrodirective reflection substrate, (2) at the bottom of described substrate lamination adaptation layer, (3) are bonding a series of refracting elements on the covering layer of substrate, (4) smooth (debossing) refracting element, form flat relatively upper surface, (5) on upper surface, apply dyed layer, and (6) embossing substrate, make refracting element give prominence to substrate.
" smooth " is meant the process opposite with embossing, even have the surperficial relatively flat of reticulate pattern.In this article, will originally depress, made it relative with substrate with high from the refracting element of substrate upper surface upper process.A kind of method of flattening comprises that the substrate that will have adaptation layer and refracting element adds in one group of roller.For example, refracting element is contacted with steel rider, adaptation layer is contacted with the rubber rollers that can be out of shape under lamination pressure, exerting pressure is pressed into adaptation layer with refracting element.After smooth, the upper surface of sheet material need not smooth fully.There are some surfac topographys to allow.Be preferably, final substrate surface is as far as possible near flush (flush) with refracting element.After smooth, with the method for any routine part substrate, part refracting element and antiskid particles (if any words) on apply dyed layer.
Before adding refracting element, also opaque dyed layer can be shifted on the selected part of substrate.For example, a kind of method that is used to prepare colored counter-reflective products, comprise the following steps: that (1) forms the retrodirective reflection substrate that comprises a series of reflecting elements and one deck thermoplastic cover layers, (2) pattern with rule forms discontinuous thermosetting polymer on covering layer, form the substrate of part printing, (3) substrate of the described part printing of heating, make covering layer softening, (4) when covering layer is softening, on the substrate of described part printing, place refracting element, make refracting element optionally thereon bonding, (5) fusion refracting element and (6) cooling.The some parts of thermosetting polymer can contain colorant as required.For example, in an example, the zone below refracting element (being the bonding zone of refracting element and emulsion sheet), but the All Ranges of substrate printing heat solidity dyed layer all.In another example, can surround the thermosetting polymer of the zone printing printing opacity of refracting element at the radius of determining.The remainder of substrate can print with another kind of painted thermosetting polymer (as white).Zone under refracting element is not printed.Because light may enter the substrate sections beyond the refracting element bottom, the light transmission polymer areas of surrounding refracting element still can make light enter substrate and by the retrodirective reflection of substrate institute.The advantage of this method is to place in an orderly way refracting element, thereby has increased the optical efficiency of goods, simultaneously the amount of used refracting element is reduced to minimum, to reduce cost.
The dyed layer composition (if any words) should be able to anti-solvent, the friction and the ultraviolet light irradiation of the anti-vehicles.An example of colourant solution comprises that 78 weight %NEOREZ R960 board water-based polyurethane resins are (available from Zeneca Resins, Wilmington, Massachusetts), 19 weight %WW3000 board titanium dioxide dispersion are (available from Heucotech Ltd., Fairless Hills, Pennsylvania) and 3 weight %CX100 crosslinking agents (available from Zeneca Resins, Wilmington, Massachusetts).Using other dyed layer component is conspicuous to the those of skill in the art in this area.
Being used in combination light tight and colorant printing opacity is conspicuous to the those of skill in the art in this area.For example, the painted refracting element of printing opacity can be placed light path and lighttight dyed layer is placed outside the light path.By this way, goods can obtain effective daytime and night color.Therefore, can use the light tight of any combinations thereof and printing opacity system.
VI. antiskid particles
Antiskid particles is the component of using always in many road surface identifications, is used to increase the skid resistance of road surface identification, and this particle is widely used in this area.They can be placed any position that contacts with vehicle tyre on the product surface.
Usually, when coverlay is in soft state, antiskid particles randomly is sprinkled upon on the coverlay of substrate.Also they intentionally can be placed on the refracting element as sharp-pointed part.Have found that antiskid particles can be placed on the top near refracting element according to qualifications.For example, useful binders composition kiss is coated the substrate web of wearing refracting element." kiss is coated with " is meant a kind of painting method, and wherein composition only is coated in the top of refracting element on request; Promptly only allow the top of solution " kiss " refracting element.Can and coiled material be remained on the top and the coating composition position contacting that only make refracting element by the gap between the control applicator roll and implement this method.When composition is when wetting, a large amount of antiskid particles is sprinkled upon on the coiled material.Because the remainder of substrate is dry, so antiskid particles only is bonded in moistening zone.Shrug off unnecessary antiskid particles from coiled material.Subsequently coiled material is sent into and carried out drying in a series of baking ovens, solidify or make wet adhesive composition to solidify.Antiskid particles optionally is fixed on the top of refracting element as a result, thereby forms skid resistance.
VII. use
Counter-reflective products of the present invention can be advantageously used in many different purposes, especially for the occasion of light with wide-angle incident.Specifically, these goods are very suitable for as road surface identification or horizontal mark.Because these goods all have high retroreflectiveness when big angle of incidence and little angle of incidence, so it can also be applicable to vertical purposes well, as is used for cattle pen or guardrail; Be applicable to curved surface purposes such as traffic tube, pipe (tubes) and cone (cones); Be applicable to vehicle surfaces; With the very effective incident angle characteristic that is used for goods be other favourable purposes.For example since the example of many reflector plates of the present invention 0 °-can both provide effective retrodirective reflection near nearly all angle of incidence of 90 °, the result, when with this sheet material during around object (isolating as telephone pole or traffic) parcel, the whole surface of sheet material in eye-level display comprises bending and the product surface part that exceeds observer's sight line can both form effective retrodirective reflection.This has increased the retrodirective reflection effective area, forms the sign of easier observation, thereby has strengthened safety.In addition, the independent sign of parallel with article one road and vertical with the second road (described second road intersects with article one road) (as the band on guardrail, cattle pen or wall, this sign sees it is opposite side on article one road from the second road) can provide very bright and effective retrodirective reflection response simultaneously to the automobile driver on article one and second road.
Another advantage of goods of the present invention is owing to can both see described counter-reflective products in many directions, and this omnibearing feature makes that the present invention is specially adapted to as level sign and motor vehicle from the sign of the approaching intersection of all directions etc.
The easy to be painted of this reflector plate also makes it be specially adapted to identify as level.The mode of transparent color layer with pattern can be imprinted on the sheet material, so that have much at one color and pattern when watching on the light of retrodirective reflection and daytime.If below superficial film, so that protect it to exempt from traffic wear with refracting element and continuous transparent solid covering layer, this printing is particularly useful with ink printing.Because printing ink commonly used approaches, this method particular importance, if make it exposing surface, it can be worn and torn by road traffic soon.
Material webs of the present invention can be become web-like.The projection that refracting element forms is not enough to influence system volume substantially.
VIII. embodiment
Below, will further specify the present invention by following nonrestrictive illustrative embodiment.
Wet retroreflectiveness
With LTL 2000 (available from Delta Light ﹠amp; Optics, Lyngly Denmark) measures the wet retroreflectiveness of reflector plate, and it measures retrodirective reflection brightness in the viewing angle of 88.76 ° of angle of incidence and 1.05 °.This angle is similar from the situation of 30 meters place experience of reflection road surface identification average out at vehicle to the driver.At first sheet material is flatly placed the trial zone, wash it with the polymer solution in water of 0.1 weight %AJAX board laundry soap subsequently.Diffluence solution carried out brightness measurement in 10 seconds.It is in order to increase the surface moist of sheet material that Xiang Shuizhong adds soap.When the reflection road surface be identified on the road place a period of time after because during the gathering the wettability that makes it and increase of the effect of sunlight, abrasive particle and sand grains and dirt, soap can also be simulated the effect of rainwater well.
The measurement of retrodirective reflection brightness
Measure the retrodirective reflection brightness of some samples according to ASTM D 4061-94.Use the described interior geometry of ASTM E 808-94.(presentation angle) is constant in 0 ° with the oblatio angle, and orientation angle (orientationangle) is remained on-180 °.
The retrodirective reflection brightness of measuring some sample in following angle of incidence and viewing angle (is retrodirective reflection luminance factor R
L, bear/m with milli
2/ lux is a unit), described angle is corresponding to the driver of 1989 Pontiac Bonneville automobiles angle of incidence and the viewing angle at four different viewing distances:
Apart from the angle of incidence viewing angle
30m??????88.5°????1.0°
50m??????89.3°????0.6°
80m??????89.6°????0.4°
120m?????89.7°????0.25°
Color measurements
CAP Y is that the colorimetry of sheet material whiteness is measured.Use Hunter spectrophotometer (Hunter MiniScan XE) to measure CAP Y according to ASTM 97-77.
Skid resistance is measured
Skid resistance is tire the measuring of tendency toward sliding on sheet material.Measure skid resistance according to ASTM E 303.
Embodiment 1
Under the standard extrusion condition, use single screw extrusion machine and sheeting die that MORTHANE Brand PN3429-215 is (a kind of available from Morton International, Seabrook, the aliphatic polyester thermoplastic polyurethane of New Hampshire) extrude on the PETG carrier.Form 50 microns (2mil) thick polyurethane surface facial mask.
Toluene-butanols mixture with 50/50 weight % will contain Q-THANE Brand QI 4820 (available from K.J.Quinn﹠amp; Company, primary coat solution Inc) is diluted to about 200cps.Use grooved roll cladding process commonly used diluted primary coat solution to be coated on the high angle performance substrate (available from St.Paul, the 3M SCOTCHLITE Brand Reflective License PlateSheeting No.3750 of Minnesota 3M company) with 150 line quadrilaterai socket grooved rollers.Have the silicone paper lining on the sheet material.(30 feet/min) speed makes the solution drying by a series of 66-121 ℃ of (150-250) heated oven with about 9.1m/min.
Use the thermometal jar (can) of heating and the pressure roll of rubber-coated that polyurethane film and pet vector thereof are laminated on the primary coat surface of high angle performance substrate.The speed of service of pressure roll be 6.1m/min (20 feet/min), pressure is that 19kg/cm is wide, temperature is 150 ℃ (300 °F).
Tear pet vector off from polyurethane film subsequently.Tear the silicone paper lining off from high angle performance substrate, stay the adhesive that exposes.(available from A.J.Oster Foils, Inc.) adaptation layer is laminated on the adhesive that exposes the aluminium foil of the No.1145-O individual layer roll-in that 75 microns (3mil) is thick, forms composite sheet.
Making aluminium foil described composite sheet be placed temperature down is the air circulation convection oven of 225 ℃ (440).After 15 seconds, open baking oven, spill cloth MORTHANE Brand L425.91 bead (a kind of thermoplastic polyurethane) available from Morton to the surface of composite sheet.Close baking oven subsequently once more, sheet material was heated 5 minutes with bead again.Taking-up applies the sheet material of bead and cooled off about 1 minute in room temperature from baking oven.
The basic thermoplasticity bead uniformly of size randomly is applied on the composite sheet.Sparsely apply bead so that make Interglobular mutual covering minimum, but have enough density to produce strong retrodirective reflection performance.The coat weight of bead is about every square metre of sheet material 300g, or every square metre of about 13,000 beads of sheet material.The original shape of bead is oval-shaped, and major axis and minor axis are respectively 4.5mm and 3mm.After the heating, the bottom surface of this bead flattens.The exposed portions serve of bead becomes circle or is spherical.The about 4.5mm height of refracting element that generates, the about 5mm of bottom width.
Aluminium foil one side with this composite sheet is laminated on the rubber-based pressure-sensitive adhesive that is suitable for being bonded on pitch or the concrete subsequently, forms counter-reflective products.This counter-reflective products is laminated to carries out the retrodirective reflection analysis on the aluminium breadboard.
To comparing, the results are shown in table 1 in all angle of incidence without the 3M SCOTCHLITE Brand Reflective LicensePlate Sheeting No.3750 of any processing with according to the retroreflectiveness of as above describing the sample that makes.The viewing angle of brightness measurement is 1.0 °, and brill is that milli is born/m
2/ lux, i.e. retrodirective reflection luminance factor R
L
Table 1: the retrodirective reflection brightness that records 1.0 ° of viewing angles according to ASTMD-4061-94
| Angle of incidence | Substrate (mcd/m 2/lux) | Goods (mcd/m of the present invention 2/lux) |
| ????-4 | ????9749 | ????10363 |
| ????10 | ????9689 | ????10245 |
| ????20 | ????9479 | ????10024 |
| ????30 | ????9433 | ????10038 |
| ????40 | ????9997 | ????10715 |
| ????45 | ????9978 | ????10721 |
| ????50 | ????9299 | ????9980 |
| ????55 | ????8676 | ????9204 |
| ????60 | ????9308 | ????8562 |
| ????65 | ????8141 | ????7998 |
| ????70 | ????7643 | ????7104 |
| ????75 | ????6205 | ????5502 |
| ????80 | ????3615 | ????3239 |
| ????85 | ????981 | ????1536 |
| ????88.5 | ????137 | ????1840 |
Table 1 shows, in the brightness unimpaired of low angle of incidence goods of the present invention.In fact, the brightness at low angle of incidence (being lower than about 50 °) goods of the present invention does not descend.Obviously at least 10 times have been increased in about 88.5 ° very big angle of incidence brightness.
Embodiment 1B
As described in embodiment 1, make the road surface identification material, but be to use every square metre of 94g bead to form every square metre of about 4000 refracting elements.
Embodiment 2
Using single screw extrusion machine that thermoplastic polyethylene-methacrylic acid copolymer (EMAA) resin (NUCREL Brand 699 is available from Du Pont) of about 50 micron thickness is extruded is coated on the pet vector.Extrusion die and extrusion condition and E.I.Du Pont Company are similar to the extrusion condition of this concrete resin suggestion.With the film heat lamination on pet vector that generates at high angle performance substrate (3M SCOTCHLITE Brand Reflective LicensePlate Sheeting No.3750; abbreviation " 3750 ") on the front surface; the front surface of this sheet material (away from the side of siloxanes protective lining) is in advance through ADCOTE Brand 50T4983 (a kind of EAA of water ballast (polyethylene-acrylic acid) is available from Morton Chemical Co.) primary coat.Add 20 parts of ethanol among per 100 parts of ADCOTE Brand 50T4983.With common grooved roll paint-on technique, use 150 line quadrilaterai socket grooved roller patterns solution to be applied on 3750 the surface, in the baking oven of the forced air convection of 93 ℃ (200) dry 1 minute subsequently, use the condition that is same as embodiment 1 will be carried on the thick EMAA film heat lamination of 50 microns (2mil) on the pet vector 3570 primary coat one side.Tear pet vector off.As embodiment 1, compact layer is pressed on 75 microns (3mil) thick aluminium foil (available from the aluminium foil of the individual layer roll-in of A.J.Oster).
In the baking oven of 205 ℃ (400), the sheet material preheating that forms after 15 seconds, is spilt cloth NUCREL Brand 699 beads (material of making the top layer film with the front is identical) on sheet material.This sheet material that has NUCRELBrand 699 beads is placed the different time in 205 ℃ (400) airtight baking oven, take out subsequently, cooling is 1 minute in water.
Embodiment 2A
NUCREL Brand 699 beads are sprinkled upon after on the composite sheet of preheating, it is placed about 45 seconds in the baking oven of 205 ℃ (400).The shape of the refracting element that forms is similar to the refracting element 42 among Fig. 6.As described in embodiment 1, composite sheet is laminated on the contact adhesive, forms counter-reflective products.
Embodiment 2B
NUCREL Brand 699 beads are sprinkled upon after on the composite sheet of preheating, it is placed about 60 seconds in the baking oven of 205 ℃ (400).The shape of the refracting element that forms is similar to the refracting element 44 among Fig. 6.As described in embodiment 1, composite sheet is laminated on the contact adhesive, forms counter-reflective products.
Embodiment 2C
NUCREL Brand 699 beads are sprinkled upon after on the composite sheet of preheating, it is placed about 90 seconds in the baking oven of 205 ℃ (400).The shape of the refracting element that forms is similar to the refracting element 46 among Fig. 6.As described in embodiment 1, composite sheet is laminated on the contact adhesive, forms counter-reflective products.
Embodiment 3
The extruded film of present embodiment is identical with embodiment 1 with carrier, but regulates extrusion condition (speed of drawing of screw rod revolutions per minute and film) so that form the polyurethane film of 250 micron thickness on pet vector.With the method that is same as embodiment 1 polyurethane film is laminated on the retrodirective reflection substrate, removes pet vector and be laminated on the aluminium foil of 75 microns (3mil).After being laminated on the aluminium foil, the composite sheet of aluminium foil backing is placed on the template of hydraulic press of heating, this template has the PET film (siloxanes PET film is available from Courtalds) of 12 microns (0.5mil) silicone coated, the polyurethane one of composite sheet faces siloxanes PET, and the thick flat supporting steel plate of about 3mm (0.125 inch) is towards the aluminium foil one side of composite sheet.With 41, the closed hydraulic press of the pressure of 300kPa (6000psi) also is heated to 190 ℃ (370 °F) with template.Before template is taken out, it is cooled to 52 ℃ (125 °F) from hydraulic press.Remove PET and abandon it.Template in the hydraulic press has and United States Patent (USP) 4,145, the raised line pattern that Fig. 2 of 112 is identical.But actual mold pressing shape is more similar to Fig. 5 herein owing to the stiffness of PET.At last, the aluminium backing composite sheet with raised line is laminated on the rubber-based pressure-sensitive adhesive.
Embodiment 4
The building method of embodiment 4 is identical with embodiment 2, still replace the film of 50 micron thickness with the EMAA skin covering of the surface of 250 micron thickness, and the polymer globules of using is SURLYN Brand 9910 (ionomer of polyethylene-methacrylic acid and zinc salt is available from Du Pont).The sheet material that will have SURLYN Brand bead heated 5 minutes in the baking oven of 250 ℃ (480), and the shape of generation is similar in appearance to the shape of Fig. 4 refracting element 44.Because the high melt viscosity of SURLYN Brand resin, bead trend towards being spherical completely; But,, thereby this spherical bead is played good fixation because capillarity makes thicker top layer can climb up the side of SURLYN Brand bead.
These embodiment that record with method noted earlier bear/m with milli
2/ lux is that the wet retrodirective reflection brightness of unit is as follows:
Table 2: the wet retroreflectiveness that uses LTL 2000 to record
| Embodiment | Wet retrodirective reflection brightness |
| ????1 | ????2300 |
| ????1B | ????1100 |
| ????2A | ????1700 |
| ????2B | ????1600 |
| ????2C | ????1400 |
| ????3 | Not test (N.T.) |
| ????4 | ????2200 |
By comparison, three kinds of commercially available road surface identification bands: 3M SCOTCH-LAne board can remove road surface identification band 620,3M SCOTCH-LAne board can remove the wet retrodirective reflection brightness of road surface identification band No.5710 and 3MSTAMARK board high-performance road surface identification band 380 all be lower than 100 millis may/m
2/ lux.
Embodiment 5
Make counter-reflective products through the following steps:
A) make polymer globules
With the feed rate of 13.6kg/hr with graininess aliphatic urethane L425.91 (according to the method A of ASTM D1238, the melt index (MI) that condition 200/8.7 records is 12) adding 34mm double screw extruder, extruder uses rotating operation method in the same way, and spiro rod rate is 450 rev/mins (rpm).Extrude with the polymer fusion and by diplopore wire rod die head, and immediately in water-bath quenching it.Blow away excessive moisture, and cut this wire rod with Conair 304 type comminutors.The speed of regulating comminutor is to form approximate cylindrical bead, length average out to 2.74mm, diameter 2.36mm., put it into high intensity mixer (91-263 type Waring blending machine) subsequently and, form single free flowable bead aging 1 week of bead in room temperature to open the aggregate of bead.After extruding, use identical method and condition to measure the melt index (MI) of bead once more, find that melt index (MI) is about 60.These beads are used to make skin covering of the surface and refracting element.
B) skin covering of the surface extrudes
With top A control bead in 54 ℃ dehumidification dryer dry 18 hours.Subsequently it is extruded by 24: 1 single screw extrusion machines of 31.75mm, the screw speed that uses is 80rpm, and melt is extruded and is coated on 0.06mm PETG (PET) film with the paint-on technique of extruding commonly used by the die lip sheeting die of living.The speed of drawing of regulating the curtain coating wheel makes the edge of the film of formation be trimmed to the wide and coating thickness of 0.317m to be about 0.1mm.With the film rolled for future use.
C) preparation retrodirective reflection substrate and adaptation layer
(QC4820 is available from K.J.Quinn﹠amp to use aliphatic urethane solution; Co.) primary coat 3M SCOTCHLITEBrand Reflective License Plate Sheeting No.3750 (being called 3750 sheet materials) available from Minnesota Mining and Manufacturing Company.With the mixture of 50/50 isopropyl alcohol and toluene QC 4820 solution are diluted to viscosity in advance and are about 200cps.Use grooved roll paint-on technique commonly used described diluted solution to be applied on the upper surface of 3750 sheet materials subsequently with 150 line quadrilaterai socket grooved roller posts, make it subsequently by 5 baking ovens (each baking oven 7.6m length, oven temperature is respectively 65/79/93/107/121 ℃, the speed of service is 30.5m/min) carry out drying, the primary coat sheet material of formation is rolled storage.3750 sheet materials that provide have adhesive and protective lining.
Use subsequently following heat lamination techniques with 3750 sheet materials of primary coat and top B control skin covering of the surface be combined with each other: the skin covering of the surface volume is opened and made it be 0.61m by diameter, surface temperature is 149 ℃ a thermometal jar (making the PET one of film face the metal can of heat).Before on the surface that superficial film is pressed in 3750 sheet material primary coats, skin covering of the surface is stayed on about quarter turn of thermometal jar.Be laminated between the pressure roll of coating rubber of a thermometal jar and a 0.2m diameter and carry out, the pressure of use is 1300 kilograms.The Xiao Er A hardness of the rubber rollers that records is 55.The width of thermometal jar and pressure roll is respectively 0.46m.The width of 3750 sheet materials of primary coat is 0.311m, and the width of skin covering of the surface is 0.317m.The surperficial running speed of all rollers all is about 9.1m/min.Compound sheet material stops 1/2 of about metal can circumference on the thermometal jar.Subsequently, it is removed from the thermometal jar, and by a water chill rolls.Work in-process is removed PET online from skin covering of the surface, the Rectroreflective sheet of formation is rolled storage.
Substrate (superficial film is pressed on 3750 sheet materials of primary coat) volume is opened, and the use thermometal jar identical with the front and pressure roll equipment is pressed in this substrate layer on the thick aluminium foil adaptation layer of 0.076mm (available from the aluminium foil of the No.1145-0 individual layer roll-in of A.J.Oster FoilsInc.), but the processing temperature of this moment is a room temperature.At first, remove the protective lining at the 3750 sheet material back sides, expose contact adhesive.The working pressure roller is pressed in substrate layer on the aluminium foil subsequently.
D) apply antiskid particles and refracting element
With C control the web substrate on aluminium foil open, with its by with C joint in identical 5 baking ovens when being used for primary coat 3750 sheet materials.Oven temperature is arranged on 232/232/232/232 ℃ and the speed that coiled material passes through is arranged on 12.2m/min.The 5th baking oven power supply is cut off.Behind first baking oven, when coiled material enters regional between first and second baking ovens with 16.7g/m
2Ratio ceramic antiskid particles is sprinkled upon on the hot rolling material.Since coiled material be heat and skin covering of the surface be soft, so antiskid particles is not by closely from the teeth outwards bonding.Immediately making coiled material enter all the other baking ovens heats.Final because the effect of gravity and capillary force closely is bonded on the softening skin covering of the surface antiskid particles, form anti-skidding coated substrates.The power supply of the 5th baking oven deliberately closed so that have cool time before coiled material rolled storage.
The web substrate of anti-skidding coating is opened, processed by identical a series of baking ovens subsequently.At this moment, oven temperature is arranged on 210/210/210/210 ℃, and web speed is 13.7m/min.Close the power supply of the 5th baking oven.,, when it enters regional between first baking oven and second baking oven, the polyurethane bead that makes in the A joint is sprinkled upon on the coiled material by behind first baking oven at coiled material.The coating ratio of bead is 138g/m
2, and it partly is bonded on the surface of hot radical sheet.Coiled material is entered heat in second and the later several baking ovens and softening, form the approximate hemispheric refracting element similar to Fig. 6 refracting element 44.Coiled material is cooled off in baking oven district 5.At last, rubber-based pressure-sensitive adhesive is applied on the aluminium adaptation layer, forms counter-reflective products.These goods are applied on the road surface, find that they all have good retroreflectiveness under dry and moistening (rainy day) condition.
Embodiment 5A
Make the sheet material of present embodiment according to the method for embodiment 5, but apply bead and form refracting element during for 9.1m/min in coiled material speed.The shape of refracting element is similar to the refracting element 46 among Fig. 6 in the counter-reflective products that forms.
Embodiment 5B
Make the sheet material of present embodiment according to the method for embodiment 5, but apply bead and form refracting element during for 19.8m/min in coiled material speed.The shape of refracting element is similar to the refracting element 42 among Fig. 6 in the counter-reflective products that forms.
Embodiment 6
Prepare counter-reflective products according to embodiment 5 described methods, still:
In the A joint, do not prepare bead.In the B joint, NUCREL Brand 699 (available from polyethylene-acrylic acid (EMAA) copolymer of Du Pont) to be extruded on identical PET lining, the temperature of telomerized polymer, speed etc. are 0.05mm so that make the thickness of film.C joint is identical with embodiment 5, but the primer that is to use is ADCOTEBrand 50T4983 (available from EAA (polyethylene-acrylic acid) copolymer of the water ballast of Morton Chemical Co.), and dilutes it with the ethanol of 20 weight %.In the D joint, do not use antiskid particles.Simultaneously, use SURLYN Brand 1702 (a kind of EMAA of ionomer is available from Du Ponts) to make refracting element.Apply rubber-based adhesive and form counter-reflective products, it is applied on the vertical obstruction of cement subsequently and (often is called " cattle pen ").Equally, under dry and moist environment, all has good reflectivity.
Embodiment 7
According to the colored counter-reflective products of method preparation of embodiment 5, but do not apply rubber-based adhesive at adaptation layer.Use the following step that this centre Rectroreflective sheet is further handled to add color:
With Rectroreflective sheet (comprising substrate, refracting element and antiskid particles and adaptation layer) in the middle of described add with embodiment 5C joint in the identical thermometal jar equipment, with the surface (refracting element and antiskid particles) of pressing (deboss) existing three-dimensional protrusion so that end face is smooth as far as possible.The thermometal jar is not done to dispose so that process in room temperature.The refracting element of middle sheet material is placed towards the metal can surface of not heating, and by pressure roll to flatten.In this process, refracting element and antiskid particles are pressed in the aluminium foil adaptation layer, and this aluminium foil adaptation layer can be out of shape owing to be close on the softer pressure rubber roller.Linear velocity is 6.1m/min, and pressure roll is arranged on 2310 kilograms, the sheet material of the pressing that forms is rolled into web-like stores.The sheet material volume that flattens is opened, used the gravure printing ink of the linear velocity printing White-opalescent of 100 line groove rollers and 12.2m/min.The pressing sheet material that makes printing is respectively 5 identical baking ovens of 65/79/93/107/121 ℃ by temperature and carries out drying.In the intaglio process, use higher nip rolls pressure so that further flatten sheet material and printing ink is applied in the zone between refracting element and the antiskid particles.The Xiao Er A hardness of pressure roll is about 70, and pressure is about 740 kilograms (using the wide pressure roll of 0.317m).
Ink composite comprises that 78 weight %NEOREZ Brand R960 are (available from Zeneca Resins, Wilmington, Mass), 19 weight %WW3000 white color agents concentrates are (available from Heucotech Ltd, Fairless Hills is Pennsylvania) with 3 weight %CX100 crosslinking agents (equally available from Zeneca).After ink coats and the drying, again sheet material is rolled into storage roll.
The pressing sheet material volume of printing is opened, used the technology identical to carry out embossing in room temperature with flattening sheet material.But, in the embossing process, the aluminium adaptation layer is contacted with the thermometal jar.When the sheet material that flattens passed through pressure roll, the aluminium surface was flattened once more, and refracting element and antiskid particles rise, and recovered near its original three-dimensional arrangement.Can be observed ink coats at the top of all refracting elements, the top of all slip-proof elements and the most of substrate flat site between antiskid particles and the refracting element.But the side of refracting element keeps and is not printed (because they are pushed in the aluminium foil), thereby has kept most of retroreflectiveness and increased the whiteness of sheet material on daytime simultaneously.Recording dried reflectivity is 768, and wet reflectivity is 670, and Cap Y is 52 (compare with the embodiment 5 of not printing, the Cap Y that it records is 47).
Embodiment 8
According to the colored counter-reflective products of method preparation till embodiment 5 to the C joints, retrodirective reflection sheet material (comprising substrate, skin covering of the surface and adaptation layer) in the middle of forming.Use the following step that it is further processed to add colorant:
Use the skin covering of the surface of sheet material in the middle of the screw thread bar pattern grooved roll white identical, the printing of opaque gravure printing ink with embodiment 7.Not printing zone by interval 25.4mm, wide for 2.8mm, cross fall be that 30 ° screw thread bar forms.Use conventional intaglio printing technology that sheet material is printed, and guarantee not have printing ink, be respectively 5 baking ovens of 65/79/93/107/121 ℃ with the linear velocity of 15.2m/min by temperature subsequently and carry out drying in Printing Zone not.The middle sheet material of this printing is rolled storage.Use 100 line quadrangle bruins to make notch board hole (cell).
The middle sheet material of part printing is spread out, and handled by same a series of baking ovens that temperature is arranged on 232/232/232/232 ℃/power-off.Between first and second baking ovens, on coiled material, spill cloth embodiment 5A control bead.In the process of the middle sheet material that bead is applied to the part printing, use to place coil back surface sheet material to be vibrated with the steel bar of the 32mm side of 1000rpm rotation.Vibrator bar is jumped all beads that are spilled into the bead that contacts except the zone with not printing on sheet material.Owing to use thermosetting ink to make that the Printing Zone is inviscid under the described conditions.Because heating makes the zone of not printing softening, makes bead optionally be bonded in the not printing of middle sheet material.Steel bar shakes unnecessary bead from sheet material, collect and reuse it.The sheet material that selectivity applies bead continues by baking oven, and bead is melt into approximate hemispheric refracting element.Sheet material cools off in the 5th baking oven that power supply is deliberately closed, and is rolled into storage roll.The product that obtains is that refracting element optionally is bonded in the not middle sheet material of the part printing of printing zone.The result of this method makes the graded that is arranged with of refracting element.
Use " kiss is coated with " technology to sheet material in the middle of described apply antiskid particles with further processing it.Kiss is coated with and comprises sheet material and lower roll to be rotated by a pair of roller coating machine in a solution tank.When producing from solution tank, lower roll the solution on the roller is scraped with control thickness with scraper.Middle sheet material makes the top of refracting element contact with the solution of the control thickness of lower roll by the fixed interval (FI) between top roll and the lower roll.This solution of a part is applied in the top of refracting element.
The ink composite that uses contains 97 weight %Neorez R960 and 3 weight %CX100.The about 0.3mm of sample path length on lower roll.After the solution kiss is applied to the top of refracting element, apply it with excessive ceramic antiskid particles overflow.Shrug off excessive particle lightly.Because printing ink remains wet at that point, antiskid particles selectively is bonded in ink area.Because in room temperature and be dry, therefore in the middle of the remainder of sheet material particle can be flicked off.Make this centre sheet material enter 5 baking oven districts that temperature all is arranged on 65 ℃.Linear velocity is 12.2m/min.Subsequently web sheet is made web-like.If printing ink is too thick this moment bone dry not, can continue dry and subsequently in cold curing.
Embodiment 9
According to the colored counter-reflective products of method preparation of embodiment 5, but be to use the following step:
The dyestuff of yellow transparent is added in skin covering of the surface and the refracting element.When refracting element is when making with double screw extruder, used painted preparation comprises 99.949 parts of L425.91 particulate resin, 0.05 part AmaplastGHS is (available from Colorchem International, Atlanta is Georgia) with 0.001 part of Amaplast red LB (equally available from Colorchem Intemational).This combination makes the reddish yellow bead with excellent transparency.
In order to make colored skin covering of the surface, preparation comprises 99.135 parts of L425.91 resins, 0.85 part of AmaplastGHS and 0.015 part of AMAPLAST Brand Red LB.The extrusion condition that is used to make skin covering of the surface is identical with the condition of embodiment 5.But the skin covering of the surface of formation has very dark reddish yellow, has good transparency.All other steps are identical with embodiment 5, and the yellow counter-reflective products of formation all has very dark yellow under dry and wet condition color on daytime has good retrodirective reflection color (color in night) in night.
According to embodiment 5 described preparation counter-reflective products, but be to use the following step:
According to A control polymer globules.Do not use the B joint.Subsequently, be laminated at C joint primary coat 3750 films and with it on aluminium foil adaptation layer and do not use skin covering of the surface.According to C joint primary coat 3750 films.Use is extruded embossing technology and is formed skin covering of the surface and refracting element simultaneously, making coverlay, with coverlay be laminated to be attached on the aluminium foil on 3750 sheet materials of primary coat.
In order to form coverlay, the following embossing casting roller that makes: use 3.175mm ball roof bit (mill) on the wheel of 0.61m diameter, to bore dark circular shrinkage hole as 1.4mm.Get out the figure of described shrinkage pool on wheel, make when forming refractor, these lens are arranged to catch the light that is incident to sheet material as much as possible tangently.The figure of vertical repetition of shrinkage pool is configured to 50.8mm at interval, can eliminate the covering between refracting element so that observe at 30 meters when (automobile headlamp is to 88.76 ° of the angle of incidence average out to of sheet material).In this pattern, also make the shrinkage pool intersection, make the resin of extruding with short as far as possible distance immigration shrinkage pool, and still keep tangentially and vertically concerning.Use 31.75mm extruder and with casting head place the pattern wheel above.Gap and the gap between die head and curtain coating wheel regulated between die lip are inserted shrinkage pool to obtain suitable pressure with melt, and make the thickness of the film between shrinkage pool reduce to minimum.After inserting extrusion resin, shrinkage pool plays the refraction element.So all refracting elements are connect by continuous symphysis.Both are combined to form coverlay.
After making, 3750 sheet materials of coverlay and primary coat are compound with following steps.At first the sheet material with primary coat is preheated to 149 ℃.On the online sheet material that is laminated to primary coat of the coverlay that forms, form the counter-reflective products that contains refracting element, its lower membrane, substrate and adaptation layer.Form during for 60rpm and bonding speed is 1.5m/min at extruder.
Comparative examples A
Use commercially available 3M SCOTCH-LANE Brand Series No.620 road surface identification (available from Minnesota Mining and Manufacturing Company) to compare.Described 620 signs are removable road surface identification bands flat, that expose lens, and it comprises (1) TiO
2Painted adhesive, microballoon and antiskid particles embed in the described adhesive, and (2) aluminium foil adaptation layer and (3) have the contact adhesive of lax supatex fabric.
Comparative example B
Use commercially available 3M STAMARK Brand Series No.380 road surface identification (available from Minnesota Mining and Manufacturing Company) to compare.Described 380 signs are long-life sign bands that profile is arranged, it comprises that (1) is become the acrylic-nitrile rubber base adaptation layer of frustum shape usually by embossing, (2) zone that vertically profiling is arranged on frustum, wherein be embedded with refractive index and be 1.75 microballoon and (3) and be used to be bonded to contact adhesive on the base material (as road).
Table 3
Embodiment 5,5A and 5B have shown the influence of the geometry of refracting element to the retrodirective reflection brightness characteristics.When refracting element have shown in the refracting element 44 of embodiment 5 and Fig. 6 near the shape of hemisphere the time, can record the highest brightness value.On the contrary, when refracting element flattens as embodiment 5A and Fig. 6 element 42, the retrodirective reflection brightness minimum that records.This trend is present in all distances of 30m-120m.In fact, compare at 30m and 120m respectively, hemispheric refracting element will well about 5-20 than the performance of smooth refracting element doubly.
| Embodiment | Retrodirective reflection brightness (R L) according to ASTM D 4061-94 | Retrodirective reflection brightness (R L) ??LTL?2000 | Color (Cap Y) | Skid resistance | ||||
| ??30m | ??50m | ??80m | ??120m | Daytime | Night | |||
| ????5 | ??2124 | ??4018 | ??6655 | ??8517 | ??2260 | ??1920 | ????47 | ????39 |
| ????5A | ??371 | ??561 | ??567 | ??405 | ??320 | ??250 | ????47 | ????41 |
| ????5B | ??969 | ??1564 | ??1887 | ??1800 | ??1020 | ??765 | ????47 | ????38 |
| ????6 | ????47 | Not test (N.T.) | ||||||
| ????7 | ??768 | ??1403 | ??2301 | ??2358 | ??750 | ??670 | ????52 | ????38 |
| ????8 | ????60 | ????84 | ||||||
| ????9 | ?1688 | ?3051 | ?4608 | ?5267 | ?1710 | ?1450 | ????31.5 | ????46 |
| ????10 | ????48 | Not test (N.T.) | ||||||
| Comparative examples A | ?949 | ?976 | ?988 | ?582 | ?930 | ?60 | ????85 | ????58 |
| Comparative example B | ?763 | ?902 | ?1020 | ?1042 | ??835 | ??110 | ????75 | ????45 |
Equally, the performance of the hemispherical refracting element of embodiment 5 is better than the performance of the approaching spherical refracting element shown in embodiment 5B and Fig. 6 element 42.As shown in table 3, compare at 30m and 120m respectively, the performance of hemispherical refracting element is than the well about 2-4 of performance times near spherical refracting element.
In addition, embodiment 5 goods are wondrously all high in the retrodirective reflection brightness of all distances.Along with the increase (promptly being added to firing angle) of distance, the embodiment of the invention 5 goods show higher retrodirective reflection performance.The road surface identification band of many routines does not all have so high retrodirective reflection performance in high angle of incidence.
Glossary
When describing the retrodirective reflection geometry herein, use following definition:
" reference axis " be on the light incidence point with the axis of counter-reflective products quadrature.
" incident axle " is by the axle that limits from light source (as motor vehicle headlamp) to the optical path of incident light the incidence point of goods glazing.
" angle of incidence " (being also referred to as β sometimes) is the angle between reference axis and the incident axle.
" observe axle " be by the incidence point on the goods to the light path of the retrodirective reflection light of point of observation (as the eyes of automobile driver) limits spool.
" viewing angle " (being sometimes referred to as α) is the angle between incident axle and the observation axle.
" plane of incidence " is the plane by reference axis and incident axis limit.
" viewing plane " is by the plane of observing axle and incident axis limit.
Under situation without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are conspicuous to the those of skill in the art in this area.
Claims (55)
1. counter-reflective products comprises:
(a) comprise a series of reflective elements and tectal retrodirective reflection substrate;
(b) be bonded in a series of refracting elements on the described substrate front surface, make the part light that is incident on described a series of refracting element be refracted, import described substrate into, by described substrate retrodirective reflection, and reflected once more, thereby make described light by described goods retrodirective reflection by described refracting element.
2. goods as claimed in claim 1 is characterized in that described at least tectal top layer and described refracting element belong to same adoption compound.
3. goods as claimed in claim 1 is characterized in that described substrate comprises being selected to embed at least a in lens retroreflective sheeting or the sealing lens retroreflective sheeting.
4. goods as claimed in claim 1 is characterized in that the retrodirective reflection brightness of described goods greater than 85 ° angle of incidence the time will be higher than the retrodirective reflection brightness of the described goods that do not have described a series of refracting elements.
5. goods as claimed in claim 1 is characterized in that it also comprises antiskid particles.
6. goods as claimed in claim 1 is characterized in that comprising the material that is selected from pottery and polymeric material to the described refracting element of small part.
7. goods as claimed in claim 1 is characterized in that comprising the polymeric material that is selected from fluoropolymer, Merlon, acrylic acid, polyester, polyurethane, polyvinyl chloride, polyolefin copolymer and composition thereof to the described refracting element of small part.
8. goods as claimed in claim 1 is characterized in that comprising thermoplastic to the described refracting element of small part.
9. goods as claimed in claim 1 is characterized in that comprising aliphatic urethane to the described refracting element of small part.
10. goods as claimed in claim 1 is characterized in that comprising polyethylene-acid copolymer to the described refracting element of small part.
11.. goods as claimed in claim 1 is characterized in that being at least 45 to the Xiao Er D hardness of the described refracting element of small part.
12. goods as claimed in claim 1 is characterized in that described refracting element has random shape.
13. goods as claimed in claim 1 is characterized in that having round profile to the horizontal section of the described refracting element of small part.
14. goods as claimed in claim 1 is characterized in that having round profile to the vertical cross-section of the described refracting element of small part.
15. goods as claimed in claim 1 is characterized in that having the basic front surface on plane that is to the vertical cross-section of the described refracting element of small part.
16. goods as claimed in claim 1 is characterized in that to the vertical cross-section and the horizontal section of the described refracting element of small part round profile being arranged all.
17. the article of claim 16 is characterized in that the contact angle of described refracting element in the bottom surface is about 45-135 °.
18.. the article of claim 16 is characterized in that the contact angle of described refracting element in the bottom surface is about 60-110 °.
19. goods as claimed in claim 1 is characterized in that the average height of described refracting element is about the 200-6000 micron.
20. goods as claimed in claim 1 is characterized in that the average height of described refracting element is about the 1000-4000 micron.
21. goods as claimed in claim 1, the mean breadth that it is characterized in that described refracting element bottom surface place equals about 2-5 times of described refracting element average height.
22. goods as claimed in claim 1 is characterized in that described refracting element is hemispheric from the part of the front surface upper process of described substrate.
23. goods as claimed in claim 1, the shape that it is characterized in that described refracting element are the shapes less than 50% hemisphere.
24. goods as claimed in claim 1 is characterized in that described refracting element contacts with surface area less than 50% described retrodirective reflection substrate.
25. goods as claimed in claim 1 is characterized in that described refracting element contacts with surface area less than 25% described retrodirective reflection substrate.
26. goods as claimed in claim 1 is characterized in that described refracting element is randomly to be arranged on the front surface of described substrate.
27. goods as claimed in claim 1 is characterized in that described refracting element is to be arranged in equably on the front surface of described substrate.
28. goods as claimed in claim 1 is characterized in that described refracting element is that figure with rule places on the front surface of described substrate.
29. goods as claimed in claim 1 is characterized in that the described refracting element of part comprises that at least one sharp-pointed part is used to increase skid resistance.
30. goods as claimed in claim 1 is characterized in that described refracting element is a frustum.
31. goods as claimed in claim 30, Yi Bian what it is characterized in that described cone is straight line at least, the contact angle of itself and described substrate is about 30-70 °.
32. goods as claimed in claim 1, it is characterized in that described substrate comprises the embedding lens retroreflective sheeting that contains the single-layer and transparent microballoon, the front surface of described microballoon embeds covering layer wherein, and at the reflection unit that is associated of described microballoon back, described refracting element is bonded on the described covering layer.
33. goods as claimed in claim 1, it is characterized in that described substrate comprises the sealing lens retroreflective sheeting, described Rectroreflective sheet comprise partly embed in the adhesive layer, single-layer and transparent microballoon that the back side has the reflecting layer, and the covering layer that places the microballoon front, described covering layer and described adhesive layer are bonded together by the network of the adhesive tape of intersection.
34. goods as claimed in claim 1 is characterized in that described substrate comprises individual layer cube corner retroreflective element.
35. goods as claimed in claim 1, it also comprises colorant in described refracting element, described covering layer and at least a in described supratectal top layer.
36. goods as claimed in claim 1, it comprises that also one deck covers to the top of the described refracting element of small part and the discontinuous layer that contains colorant on the part of the covering layer between the described refracting element.
37. be applied to the goods of the claim 1 on the road surface of motorway.
38. be applied to the goods of the claim 1 on the vertical exposing surface that is selected from guardrail, cattle pen, building wall, fence, public utility bar, traffic cone and vehicular sideview.
39. goods as claimed in claim 38 is characterized in that the described surface of at least a portion is a curved surface.
40. a method of making counter-reflective products comprises:
(a) formation contains a series of reflective elements and tectal retrodirective reflection substrate;
(b) bonding a series of refracting elements on described tectal front surface, the light that feasible part is incident on described a series of refracting element is refracted, to import described substrate into, by described substrate retrodirective reflection, and reflected by described refracting element once more, so that make described light by described goods retrodirective reflection.
41. method as claimed in claim 40, it is characterized in that described bonding a series of refracting elements comprise is placed on the thermoplastic resin bead on the front surface of described substrate, heat described bead subsequently and make described little deformation of ball, form described refracting element, then refrigerated product is bonded on the described front surface described refracting element.
42. method as claimed in claim 40 comprises and makes skin covering of the surface and described a series of refracting element simultaneously forming coverlay, and described coverlay is laminated on the described substrate.
43. method as claimed in claim 42 is characterized in that forming described coverlay and comprises and extrude embossing.
44. method as claimed in claim 42 is characterized in that forming described coverlay and comprises curtain coating and solidify processing.
45. method as claimed in claim 40 is characterized in that also comprising that at least one sneaks at least a colorant in the described refracting element, sneaks at least a colorant in the described covering layer or at least a colorant sneaked into the step that is formed in the described supratectal layer.
46. a method for preparing colored counter-reflective products comprises:
(a) be formed on and contain a series of reflective elements on the first type surface and comprise tectal retrodirective reflection substrate;
(b) the described first type surface to described substrate applies adaptation layer;
(c) bonding a series of refracting elements on described covering layer;
(d) smooth described refracting element forms flat relatively upper surface;
(e) apply dyed layer to described upper surface; And
(f) the described substrate of embossing makes described refracting element give prominence to described substrate.
47. method as claimed in claim 46 is characterized in that described colorant comprises the polymer of anti-solvent, the wearing and tearing of the anti-vehicles and ultraviolet resistance.
48. method as claimed in claim 46 is characterized in that described dyed layer comprises opaque colorant.
49. a method that is used to prepare colored counter-reflective products comprises:
(a) formation comprises a series of reflecting elements and the tectal retrodirective reflection substrate of one deck;
(b) apply one deck thermosetting polymer to a described tectal part;
(c) the described covering layer of heating makes it softening;
(d) place refracting element, refracting element optionally is bonded on the described softening covering layer;
(e) the described refracting element of fusion; With
(f) the described covering layer of cooling makes it sclerosis.
50. method as claimed in claim 49 is characterized in that described covering layer and described refracting element comprise thermoplastic polymer.
51. method as claimed in claim 49 is characterized in that described thermosetting polymer layer is a printing opacity.
52. method as claimed in claim 49 is characterized in that described thermosetting polymer comprises the colorant that is selected from printing opacity colorant and opaque.
53. a method for preparing colored counter-reflective products comprises:
(a) formation comprises a series of reflecting elements and tectal retrodirective reflection substrate;
(b) apply dyed layer to a described tectal part, form the substrate of part printing;
(c) extrude skin covering of the surface and refracting element simultaneously, form coverlay;
(d) in the mode of alignment that the substrate and the described coverlay of described part printing is laminated together, make described refracting element be positioned at substantially in the described substrate achromatization district.
54. method as claimed in claim 53, the preparation that it is characterized in that described coverlay comprises extrudes embossing.
55. method as claimed in claim 53 is characterized in that the preparation of described coverlay comprises curtain coating and solidifies processing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96195159A CN1189867A (en) | 1995-06-29 | 1996-06-27 | Wide range vertical retroreflective delineator and method for making it |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60/000,706 | 1995-06-29 | ||
| US60/000,707 | 1995-06-29 | ||
| CN96195159A CN1189867A (en) | 1995-06-29 | 1996-06-27 | Wide range vertical retroreflective delineator and method for making it |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1189867A true CN1189867A (en) | 1998-08-05 |
Family
ID=5129023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96195159A Pending CN1189867A (en) | 1995-06-29 | 1996-06-27 | Wide range vertical retroreflective delineator and method for making it |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1189867A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104011296A (en) * | 2011-09-22 | 2014-08-27 | 弗林特贸易公司 | Anti-skid high retroreflectivity preformed thermoplastic composites for runway applications |
-
1996
- 1996-06-27 CN CN96195159A patent/CN1189867A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104011296A (en) * | 2011-09-22 | 2014-08-27 | 弗林特贸易公司 | Anti-skid high retroreflectivity preformed thermoplastic composites for runway applications |
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