CA2129983C - Launderable retroreflective applique with improved retention of retroreflective elements - Google Patents

Launderable retroreflective applique with improved retention of retroreflective elements Download PDF

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Publication number
CA2129983C
CA2129983C CA 2129983 CA2129983A CA2129983C CA 2129983 C CA2129983 C CA 2129983C CA 2129983 CA2129983 CA 2129983 CA 2129983 A CA2129983 A CA 2129983A CA 2129983 C CA2129983 C CA 2129983C
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Prior art keywords
applique
binder layer
retroreflective
binder
layer
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Expired - Lifetime
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CA 2129983
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French (fr)
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CA2129983A1 (en
Inventor
Wu-Shyong Li
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3M Co
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Minnesota Mining and Manufacturing Co
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Classifications

    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/12Reflex reflectors
    • G02B5/126Reflex reflectors including curved refracting surface
    • G02B5/128Reflex reflectors including curved refracting surface transparent spheres being embedded in matrix
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/913Material designed to be responsive to temperature, light, moisture
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/252Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256Heavy metal or aluminum or compound thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/28Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31663As siloxane, silicone or silane
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/654Including a free metal or alloy constituent
    • Y10T442/657Vapor, chemical, or spray deposited metal layer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/674Nonwoven fabric with a preformed polymeric film or sheet
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/674Nonwoven fabric with a preformed polymeric film or sheet
    • Y10T442/675Ester condensation polymer sheet or film [e.g., polyethylene terephthalate, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/699Including particulate material other than strand or fiber material

Abstract

Retroreflective appliques comprising a monolayer of retroreflective elements partially embedded in and protruding from the front surface of a binder layer and an optional layer of adhesive on the rear surface of the binder layer, wherein the binder layer comprises one or more flexible polymeric binder materials having active hydrogen functionalities and one or more isocya-nate-functional silane coupling agents.

Description

"''~?JO ~3/20~t63 2 ~. ~ 9 9 ~ 3 P~d'/U~93100782 _1_ LAUN ERAB E R OR FLECT VE APPLI UE ~rllT~i IMPROVED
~~'fEON OF RETROREFLECTIVE ELEMENTS
Field of Invention The present invention relates to novel retroreflective applic~ues and articles to which such applic~ues have been applied.
BackcLround In order to improve safety of pedestrians, joggers, workers on roadways, etc., retroreflective markings have been attached to clothing. In one common 1~ embodiment, retrorefl~ctive-appliques comprising a monolayer of r~troreflecture elements (a. g., transparent microspheres with hemisphere': reflectors) par~.ially embedded in a layer of binders material', with adhesive backings are bonded to articles of clothing.
~0 In other embodiment, the aPPlic,~ues are sewn onto a w~ubw~'Itrates ~ problem with such appliques is that their retr~r~flective perfox~aaance tends to diminish unacceptably when the garment t~ which they are applied 25 is gashed. ' Aftsr just a few washing, the retroreflective brightness of the applaque may be reduced to a small fraction, e.c~. , ~ percent or less, of its ~riginal brightness. This decrease is due to loss of retroref lective ehements f~com the turf ace of 3~ the apPligu~ and/or degradation ~f the retroreflective ele~~,n.~~, a ' g ~ . coxrosi~n of alu~~.hum hemispheric reflectors, during wash~:ng~s a rosult the visibility of the appl~.que is reduced, thereby a.mpairing th,e I safety ~ of the raearex .
3~ Tie pr~blem is Parta.c~alarly troublesome when the clathing is subjected to inde~strial laundering, where the conditions of laundering are often more sevexe than conventional home laundering. For instanoe, in an iradustxial laundry, the laundering ~p conditions may include wash temperatures of ~0° to 90°C
X105° to 190°F) and pH ~f 1~ to 12.5, whereas in ~o ~~~xoa63 ~crms~3o~o~~z~..<, 2~.2~9~3 contrast, typical conditions for home laundering may include temperatures of 4° to 60°C (40° to 1~0°F) and p~I of less than 11. Also, home laundering equipment typically subjects the articles being cleaned to less rigorous handling and stress than does industrial laundry equipment.
In some embodiments, o~ganosilane and/or zircoaluminate coupling agents~whave beex~_used to ianprove the adhesion of the binder material to the retroreflective elements. Illustrative examples of previously known coupling agents include vinyltriethoacysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptdpropyltrimethoxysilane, 1.5 gamma-glycido~cypr~pyltrimetho~cysilane, gamma-aminopropy3ariethoxysilane, gamma-~minopropyltramethoacysilane, N-beta-(aminoethyl)-~~m~a-aminopropyltrime~thaxysilane, triaminofunctional tria~etho~ysilane, ~.mim~ functional zircoaluminate.
2~ carboxy functional zircoalumin~te, and mercapto furaGtional xa~rcoaluminate; used singly or in combination. Selecti~n of c~upli~g agents) is dependent ~n p~~t uponvthe hinder material and retroreflective elements used: Ta minimize fading of 25 aluminum reflector layers, it is typically preferred that ~a~ino~con~sining silane coupling agents be avoided. Mercapt~func~tion~l silane c~upling agents typi.cal~.y exhibit a very objeeti~nable odor. Done of these ~oupla.x~g agents p~rfo~s as we3:1 as desired in ~~ refi~roreflective appliques eubjedted to ia~dustrial wash condit'ionsa Summer of 7~nVe .The present invention provac~es novel ,35 retx~o~eflective appliques wh~.ch can be applied to substrates such as fabrics and garments to impart retroreflsctive properties thereto. Appliques of the invent~.ori provide unexpected durability. Capable of being applied to fabric substrates, appliques of the '''V~ 931Z~D463 _ 212 9 ~ 8 3 pCI'/gJS93/Qi37~2 invention exhibit surprising resistance to degradation when the article is laundered and retain a surprising degree of retroreflective properties. -In brief summary, a rezrorez~~~:L.~y~ ~rr~~~u~=
of the invention comprises a monolayer of retroreflective elements partially embedded in and protruding from the front surface of a binder layer and, an optional layer of adhesive, preferably hot melt type, on the rear surface of the binder layer. Prior to application to a substrate, typically fabric such as a f lag or garments the adhesive layer is optionally covered with a removable release liner. In some embodiments, the-~applique is bonded to a substrate with the optional adhesive, and in other embodiments the binder layer serves to both secure the retroreflective elements and to bond the applir.~ue to a desired substrate. If desired, the applique can be sewn onto a fabric substrate.
Appliques of the invention differ from those available bef~r~ in that the binder layer comprises one ox moge flexible p~ly~aers having active hydxogen functionaliaa.es such as crosslinked, flexible urethane-~as~d polymers (a,g:, isocyanate-cured polyesters or one ~r two component polyurethane, and one or more a5 is~cyanate-~fun~tional silane coupling agents.
Retror~f lective ap~~.iques of the in~renta.on have been found to exhibit surprising retention of r~tr~reflective brightness, even when subjected to industrial Laundering conditions. This advantageous 30 _ result is achieved through a ccrmb~:nata.on of increased re~ist~ance to 1~ss of retroreflective elements and an increased resistance to degradation of the r~troref le~ti°ve elements, e:a., degradation of the reflector layer. As a result, articles to which ~5 appLiques of the invention have been applied may be laundered many more times than previously possible while still retaining desired retroreflective Gharactero -3a-According to one aspect of the present invention, there is provided a retroreflective applique wherein the applique comprises a monolayer of retroreflective elements partially embedded in and protruding from the front surface of a binder layer and said binder layer comprises a flexible polymer having active hydrogen functionalities and one or more isocyanate-functional silane coupling agents.

V~'~ 93/20463 PC I'1US93/007~2,.~~~~~

Brief Descriution of Brawinet The invention will be further e~cplaaned with reference to the drawing, wherein:
Figure 1 is cross-sectional illustration of a portion of an illustrative embodiment of a retroreflective applique of the invention; and Figure 2 is cross-sectional illustration of a ' portion of another illustrativew embodiment of a retroreflective .app~ac~ue of the invention bonded to a substrate.
These fagures, which xre idealized, are not to scale and ire intended to be merely illustrative anc~
non-limiting.
Betai ed esc ' t,o o t ative Em odi~oaents Reference is made to Figure a wherein ist shown an illustrative er~bodi~ent of ~retroreflective applique 1~ ~g the invents:~n. l~pplicyue 1~ comprises a monolayer of ~etrorefl~cti.ve elementss 12 partially embedded in and pr~truding from front-surface 14 of binder layer 15a I~i~posed on rear surface 18 of binder layer 16 is captional adhesive layer 20. Appl.~c~'ue 1~0 is shown with optional release finer 22' which covers the es~posed surface eat adhesive layer 2~To apply aPPl~.~e 10 to a substra'~e such ~s a fabric ~nc~t sh~wn) , release liner 22 is f ir~t r~:moved. Appli~.e 1~ is shorn with o~ati~onal temp4rary carrier 8 comprising paper sheet 4 and polymer l~nln~ ~ a Figure 2 shows retroreflective appligue 1~D on ~~bstrat~.~~~, ee~a, ~an art~ch. of.~loirhdng such as a j ac~Cet Or Vest .
In brief sbm~aary, ~ typical ~aethod ~f m~Dcing appliques of the invention c~mpxises arranging retr~reflective ele~aents in desired monolayer arrangement on a temporary carrier kith the rear portions of the retr~reflecti~e ~len~ents presented away from the carrier; forming a Iainder' layer over the rear portions ~f the retroreflective elements, and applying .: -:«;: , ,; :. : ;..
', , , , . . . : , . ,, . ~. : . :,::.. .... . : . :. ,. , , . . . .
,. . ., : ;:. , , .. :~... _.,., ,.. . ~.., ... ..... .. ....,: ....... , . ,.
. ....,. ..
2 ~ 2 9 ~ ~ ~ ~'~/US93/OU782 ......~i7V(~ 93/ZU~lCr3 an optional adhesive layer on the back side of the binder layer.
The most typical form of retroreflective elements ~.2 will be spherical microspheres 24 having reflectors 26 on the back sides thereof as shown in Figure ~.. As known to those skilled in the art, one method for assembling a monolayer of such , retroreflectiwe elements is to cascade microspheres onto temporary carrier 8 which secures microspheres 24 lm in desired arrangement temporarily. For instance, microspheres 24 can be partially embedded in heat softenable polymer layer ~ on paper sheet 4. Some examples of useful polymer coatings include polyvinyl chl~ride, p~lysulfones, polyalkylenes such as 1~ polyethylene, po~.ypropylene, and polybutylene, polyesters such as polyethylene terephthalate, and the l~.ke. ilpon cooling, polymer layer 6 retains mic~.osphexe~ 24 in desired arrangement. Depending in part upon the characteristics of carrier 8 and elements 2~ a2, it may be desired to coa~dition carrier 8 and/or ele~aents l2 to achieve desired release properties. For instance, selected release agents ox adhesion promoters may ' he used .
Microspheres 24 are typically preferably 25 p~Gked ~s closely as possible, ideally in their closest h~exag~nal arrangement, to achieve greater re~roxefl~ctive brightness and may b~ so arranged by a~~ay c~r~wenient ~lPPlique process, such ~s printing, careening, cascadia~g, ~r with a hot can roll.
3~ Tr~ns;~a~rent microspheres having reflectors on the rear surfaces thereof as shown in Figure 1 typically provide satisfactory levels of retr~reflectiv~ brightness over a wide range of incidence angles, i.~», the angles at which the light 35 strikes the sheeting, a proper~.y sometimes referred to as i~c'1ng'illarlty~/ .
if transparent microspheres are used, the microspheres are preferably substantially spherical in shape in order to provide the most uniform and c i~V~ 93/20463 2, ~ ~ ~ ~ ~ ~ PCT/US93/0078 . ~;~

efficient retroreflection. Furthermore, the microspheres are preferably substantially transparent so as to minimize the amount of light absorbed by the microspheres and thereby optimize the amount of light which is retroreflected by sheetings of the invention..
The microspheres are typically substantially colorless, but, may be colored to produce special effects if desired.
Microspheres used herein may be made from 0 glass or synthetic xesin having the optical properties and physical characteristics taught'herein. Glass microspheres are typically preFerred because they typically cost less, are harder, and exhibit superior durability to microspheres made of synthetic resins.
Microspheres used in the present invention will typicaiiy have an average diameter of_.betweea about ' 30 and about 20~ mi.crons~. Ma.crospheres which are smaller than this range may tend to provide-lower levels of retroreflection because of diffraction effects, whereas micrs~sphares largen than this range may tend to impart undesirably rough texture to the applique or undesirably reduce the flexibility thereof.
Microspheres used in the present invexation will typically have a refractive index s~f between about 1.7 ~5 and abaut 2.0,'the raa~ge typically considered to be useful~in microsphere-based retroref~.ective products where,: as here,: the front surfaces of the microspheres are exposed or air-incident.
As mentioned above, ~nicrcrsphere-based retroreflective elements of re~roref~ective appliques of the invention have reflectors ~n the rear surfaces thereof. y'ypically, such reflectors are app~.ied ~to the rear surfaces of the microsph~xes after the mi:arospheres have been partially embedded in the cerrier, thereby facilitating °~he arrangement of the microspheres in substantially ~n~~e~ direction for retroreflection. Furthermore, as xs known, the size of ref lectors, i . ~ . , ' how much of the' surface of the microspheres which is c~vered, may be controlled in .. .,~,0 9~oz~~63 212 9 9 8 3 P~rlu~~~ioo~s2 part by controlling the depth into the carrier to which the amicrospheres are embedded prior to application of the reflectors thereto.
,Among the variety of materials which may be used as reflectors are vacuum-deposited or vapor-coated metal coatings, such as aluminum or silver;
chemically-deposited metal coatings, such as silver; .
metal-coated plastic films; metal flakes; such as aluminum or silver; and dielectric coatings. ~lumfnum or silver coatings are typically preferred, because they tend to provide the highest retroreflective brightness. The reflective color of silver coatings is typically preferred to that of aluminum coatings, but an aluminum vapor coat is normally more preferred, 1.5 because silver xeflective coatings typically suffer more severe degradation in ou*~door eacposure than do aluminum c~atangss ~sSe PatPrnt ~lo. 3,'00,305 (B~.ngham) discloses dielectric mirrors or coatings tha°:.~nay be used as reflectors in setroreflective articles of the ~0 invention.
An advantage ~f dielectric reflectors is that applicgues jade with m~.crospheres having such reflectors gay lae easily made in a variety of bright colors. such reflectors are typically subject to degradation under 25 laundering conditions, particularly industrial ~.aundering conditi~ns, and are accordingly used on ,articles destined f~r home laundering. P.luminum and silver ref7.ectors typically ~~ibit substantially ~~.,~ater dua~ab~.lity under iaadustrial laundering 30 cdndi~ions, bud ~lumiriaam refiectors often tend to impart a gray ~~1~~ tb the appligue under ambient conditions.
Foll~wing arrangement of reflective elements 12. a comg~saaion forming binder layer ~.6 is applied 35 the~eover. bender layer 16 is typically between about 50 and about 250 microns ~2 and 1.0 mils) thick over the embedded po~ti~n of retroref~ective elements 22, with thicknesses of between about 75 .and about 1.00 macrons ~3 and ~ mils) typically being preferred. It will be PCT/U593I007~2~
. .
W~ 93/20463 ~ ~~

~8-understood that binder layers having thicknesses outside these ranges may be used. However, if binder layer 16 is too thin, it will not provide sufficient support to retroreflective elements 12 which may be readily dislodged, whereas increasing the thickness of, binder layer 16 leads to increased cost for applique 10 as greater amounts of the binder material are required..

Furthermore, at greater thicknesses the flexibility of applique 10 typ~.ca~.ly tends to decrease.

Binder layer 16 may consist essentially of one or more binder materials and one or more coupling agents as discussed herein.

Illustrative examples of suitable binder materials include isocyan~te-curable polyesters such as copolyester resins sold-in the VITEZ~ series by Goodyear Tire and Ttubber Company and polyester resins sold in the B~STZK~ series by Emhart Corporation.

Suitable binder zn~teri~ls also include such polyols as polytetramethylene oxide glycol, polyester polyal, hydroxy-Germinated polybutas~ierae, pc~lycaprolactone polyol, p~lybutylene oxide, glycol, and polypropylene 'oxide glycol. ~thers illustrative examples include the aliphatic and aromatic polyisocyanates sold in the DESMODUR~ and MQNDL1R~ series by Mobay Company.

Binder layer 16 further comprises one or m~re isocyanate-fur~ational Coupling agents ~e.g., gamma-isocyanatopropy~triethoxysi3ane) to pr~mote adhesion of binder 'layer 16 t~ retroreflective elements 12s The coupling agent() may be applied, e.g., by . spraying orc~ating, to the'surfaces of the retrareflective elements ar to the binder layer prior ', ' ' ' ~ ' to its ' apPlicati.on to the elements or mar be incorpora.te~ directly into the binder composition.

Application' to the elements provides tl~e advantage of using lesser q~aantitie~ of coupling agent, which in some instances is relatively eerrsive, whereas in~orp~ration into the binder composition provides the ad~tantage ~f eliminating ~ separate application process during fabr~.c~ation of the retroreflective applique.

P(.°I'f U~93/00?82 .. ~y.~pr~p 93/20463 Typically, an amount of isocyanate-functional coupling agent(sj an stoichiometric excess to the active hydrogen-containing binder materials) is used.
Generally, the higher the molecular weight of the coupling agents) employed, the greater amount of such agents reguired in order to attain the desired excess of isocyanate groups for linkage with the binder material. Typically, binder layer 16 will contain up to about l0 weight percent, and preferably between about 0.~. and about? weight percent, of coupling agent. If too little coupling agent is used, the resultant applique may, depending upon the characteristics of the binder material, tend to undergo undesirable loss of retror~flective elements. If too ~,5 mucl2. coupling agent is used, it may in some instances impair the physical properties of the binder layer, e.g., cause the binder layer to swell. Also, the coupling agents are typically relatively expensive as compared to the other coanpnnents of the appligues.
20 ~ As mentioned above, appliques of the invention may be set onto suDastrates if desired. In some aPPZ~-canons, h~wever, it is desired to secure the applique to the substrate by adhesive. Accordingly, in some embodiments, apPligue~ of'the invention will have 2~ an adh~sive'layer do the back sale of the binder~layer.
The adhesive is se~eated to provided suitable adhesion yproperties ~f the binder layer and the intended substrate, pref~ra~bly taking into account the cohditions to ~rhich the applique and substrate wa~l~. be 3a subjected, a~g.~ high humidity, low temperature, etc.
In some embodiment, the adhesive layer may be a layer og the''saine composition used t~ form the binder layer which is not fully cured until the app7lic~ue is contacted to a 'substrate. Preferably the binder layer 35 is sufficiently cured prior to application of such an additional lager and/or aPplica~ion to a substrate to f~dilitate handling of the appligue and ensure retention ~f the retroreflective elements.
Alternata:vely, the adhesive .layer may be of a different ____.__..... .._.m....",.,.a........,....~mmmurv.........u 8i~fi'~WiY:TFSF:.'~45~ '°'..:~PMaN,.'~-..

BYO ~3/~0463 ~ Pt.T/tJ~9310078~.;
_10_ composition. Tf desired, pressure-sensitive adhesives or activated adhesives (e. g., heat-activated, ultraviolet-activated) may be used. For instance, an iron-on applique may be provided by using a layer of suitably melting thermoplastic material.
under layer ~.6 may av~o contain one or more optional additives such as colorants (e.g., pigments, dyes, metal flakes), fillers, stabilizers (e. g., thermal stabilizers and antioxidants such as hindered phenols and light ~tabi.lizers such as hindered amines or ultraviolet staDailizers)', flame retardants, and flow modifiers (e. g., surfactants such as fluoropolym~
silicones). Preferably the additives are resistant to degradation or leaching out of the binder layer during 15 laundering;
The binder layer typically contains colorant (e.~.. Pients or dyes) to camouflage discoloration of the binder material and/or impart desired ambient color appearance to the applique. Typically a black colorant 20 is preferred because it provides the most effective camouflage c~f disc~1~ration ~f the binder material. An ~pplic~a~ compris ng microsphere~ with aluminum reflecte~rs a~ retrorefle~tiv~ elements and black colorant will typically exhibit a pleading silver 25 appearance. Preferred c~lorants for a~ppli~gues with xe Elective ~lemea~ts having alaa~inum reflector layers are black dyes, .~.g., ~aetal-a~~'dyes such as ~gir~mium-azo dyes. The binder layer typically contains between about 0:~1 and about 2:~.w~ight percent, 3~ preferably between about 0:~. anti about 0.~ weight percent of dye .
I
~xaIlt,~les The invar~tion will be further explained by the gg gall;~a~ring ialu~trative examples-which are intended to be aio~°-limiting< Unless 'othe~rise indicated, all amounts are expressed in Parts by weight.
~~l~ss otherwise indicated, the following test methods were used.

°
~WO 93/2063 2 ~ 2 9 9 8 3 PC'~'/iJ~93/007~~

after lamination to a fabric, the temporary carrier was stripped from the front of the subject appligue to reveal the silver colored retroref lective surface, retroreflective brightness was measured using a retroluiainometer as described in U.S. defensive publication T987,003 at divergence angles of about 0.2°
and entrances angles of about °4°. , Zaunderability of appliques was evaluated by washing a piece ~f fabric to which the subject applique 1.0 had been applied for the indicated number of cycles in a commercial Milnor System 7 Washing Machine Model 30015M~G from Pellerin Minor Corp. using program no. 7 for heavily soiled, colored fabric with the indicated detergent. Each cycle was about 1. hour in length. The washer was loaded with from one to four pieces of fabric (abe~ut 2 feet by 3 feet (0.6 meters by 0.9' meters) in sire) having several (typically ten or more) appliques of the invention about 2.~ by 1.5 centimeters (1 ~y S inches, in size sewn or bonded thereto and used ~o ab~ut ~~ liters (~.~ ga~:Zons) ~f water at 7~°c (~s~°F) .
Unless otherwise indicated, the cleaning agents used mere 30 grams of F~CTOR~ Detergent (from Fabrilife Chemical , Irec. containing ~tetrasodium pyrophosphate, nonylphe~ao~goly(ethylene~~cy)eth~nol, sodium carbcana~e, and silica; and 90 grams'of ~TRP,SIL~ (a pH buiYder from Feninwalt Corp. believed to cor~taa.n 40 weight percent NaO~H and SO.weight percent sodium metasilicates). The retr~refledtive brightness of the ~i~dl,e of each saa~p~.e was determined periodically. The 30: resu~.ts aree~rpressed below as the percentage of its initial retroreflective brightness the sa~rple retained after ~t~ae ~;ndicated number ~of wash cycle.
Examx~le ~ 1. ;end C-~omtive example 1~1 g5 Glass micr~spheres ~ayinc~ an average diameter of about 40 to 90 microns were partially imbedded into a temp~arary carrier sheet aa~d al,umia~um specular reflective layers ~pplasd to the e~cposed portions of the microspheres to yield'retroreflective elements.
___.................. ... .,..........-. . -.<., ..e,. r.r.......ef ... ,e ...f. na .n... e,7.e.,s~., . ., ...:_.'r.~. ' W 1. rs....r a 17.:.n~.. .. , ...

W~ 93/20463 ~ ~~ ~ ~ ~ ~ ~'G°~'/U5931007~~.~>~,~~~

A binder composition comprising:
ount Comuonent 100 Minder Material - 50 weight percent solids solution in methyl ethyl ketone/toluene ~ (1:1 weight ratio) of vVI~'EL~ vPE-5545, a linear saturated polyester from Goodyear;
2.4 finder Material -vMCNDUR~ CB75, a 75 weight percent solids solution in ethyl acetate of an aromatic pol.yisocyanate based do adduct of toluene diisocyanate, from Mobay Chemical Com~any~
2.0 Coupling Agent - ~JNI~OI~ CA~IDE~ Y9030, a gamana°isocyanatopropyatriethoxysilane; and 0.2 Catalyst - dibutyltindilaurate;
was coated over the retr~reflective elements to a wet thickness of about 175 micr~ns (7 mils) and dried at about 66°C~ (1.50°F) for 5 minutes then at 107°C
(225°~') for another 5 m3nut~s to yield a binder layer. An additional layer of the same composition eras then applied to a wet th~.ckn~ss of about 200 microns (~
~il~) to act as an ~~dhe~i~e layer.
The resultant raft~r~flective app~.iquer referred to as Example 1, eras thin wet laminated to a polyester fabric (S-551-060 from Milliken ~ Company, a 3 .11 once f yardz ( 105 ~/~2) textile polyester) ansl the con~tructi~r~ dried end cured at ~6~°C (150°~') for 5 minutes and'then at 107~C (225°F) for 5 minutes.
I1'1 (:omp~ratlve ~~Camp~.~ Pa, an a~p~l~u~ ipTa~ made as in ~5~amp7:e 1, except 2 part; Of U~II~N IDES
~0 Y94~2, an a~ino~fun~tior~al silan~, was used instead of the'is~cyanate-functional c~upl~:ng agent and the amaunt o f C~7 ~ was ~.ncx eased to 4 . 3 parts to ac~om~sodat~ the active hydrogen in the ubstit~at~ coupling agent.
The appliques of experiment ~. and Comparative ~xp~ria~ent A had initial r~'~roref~.ective brightn~sses in candelas per s~guare meter per lux ("cpl") of about 600 and 5913, respectively. The launderability results olatained are tabulated a~n' Table I r ., "''~~ 93/20463 ~ ~ ~ ~ (~ ~ ~ ~crrus93OOO782 ~~~~e I

C c es x~

67 ? ~.

5 ~ 10 46 13 .

~5 33 ~2 10 ~ ,after 5 to 10 washes, the samples of Comparative ~xperi~nent 1~, were observed to have undergone slightly more loss of ~nicrospheres; and much wore severe corrosion ~f vapor coat, than had the sazaples from Example ~..

15 These r~~ul.ts illustrate the superior launder~.bility of retroreflective appliques of the invention as comported to conventional applique~

c~ntaining c~nveratior~~l coupling agents:

~o ~m a ~ ~ ~ at've m a Tn ~~camp7.e- 2, ata app3.~:qus was made as in E~a~p~.e 1, except it eras:~ddition~lly cared at a:o?c ~~25~') for ~o minutes ~~~lowin~ the wit lamination to ~;he polyester fabric and drying and cuxingp In 25: Comp~ratave ~~caxnple B, an applie ~a~s ~oaad~ as ire Example ~ e~tc~pt ~ parts of I3C?W COI~IIvT~Z604O A axe ~po~rfuncti~a1 ~ilane, was used a~ tie oo~plirag ~gen~.

~'h~ app~a.t~~~ i~ ~3Ca~6ple 2 3Tlld l:o1d1~8~tra'~lvE:

3~ E~cample ~ had initial retrorefl~~~ave brightness~s in candelas' pE:r st~11~7C'e ~tte~' ~ her 1'tlX ( ~~Cplea ~ fJf abO7Lit 600 end 608 ~, respectively. ~'he lauraderability result tabulated ~.n -able ~~.: were .obtai~ede '..~ab~~. ~~ .

35 ~ es x. B

t3 1.00 100 80 6~

10 53 ~5 15 3~ 16 4~ 2p ~1 ~,3 2~.y~J~~~~
.:, ~V~ '~3/Z0463 - F(.Tf US93/0~782- .

~~amnle 3 end Comparative Examxale C
To make Example 3 a monolayer of retroreflective elements was prepared as in Example 1.1~
binder composition comprising:.., .
ou t ~ component 150 Binder Material -~~.5~0 weight percent solids solution in methyl ethyl ketone/toluene mixture ( 1:1 weight ratio) of vITE7L~ vPE-5545;

62.5 Binder Material - 40 weight percent solids solution in methyl ethyl ketone of polyol based on polytetragnethylene oxide having hydroxy,equivalent weight of 3000;

4.0 Coupling agent - Y9030;

4 : 5 Binder Material - ~IOIdDUE~ CB7 5 ; and 0 a~~, Catalyst w d~.butylt~.nda.~aurate;

eras coated over the al~inu~n--coated microspheres to a yet thickness ~f about 175 microns (7 mils) and dried at 66C (150~1F) for 5 minutes then at 107C (225F) for ~ minutes t~ yield the binder layer. An additional layer ~f the same composition was then Coated at a wet ~.hickness of about 200 ~a~.crons . (6 mils) . The construction was r~ret laminated to a polyester fabric ~i~e that ueed in Example ~. andl dried and cured at 66C

(150F~ for ~ min~ztes and at 107C (225F) for 5 minutes.

Tn Comparatiue Example C, an applique was made as in, Example 3 except DaW G~1RN1B'G~ Z6~D40 o an epoxy_ functional silane, was used es the caupling agent.

3'p: The applicgues i~ Exaanple 3 arad C~aap~rative Example C

had anitfal retroref lective bra.gk~tnesses ( in cpl ) ~f about 594 and 582, resp~Ctively~. The launderabil'ity resultstabu~ated Ln Tab~e~~~ ~~..re ~b~a~.neda ~~

Cycles ~ 100 180 PCTl~7S93/007~2 '°~%'~ 93120463 Exa les 4 And 5 d Com a ative am 1.e D
To male Example 4 a binder composition comprisings Amount Compcanent 100 ' Binder Material - 50 weight percent solids solution an methyl ethyl letone/toluene mixture (1:1 weight ratio) of VgTEL~ VPE-5545;
2.0 Coupling Agent - Y~030;
2.4 Finder Material - ~iONDUR~ 0875;
0:2 Catalyst - dibutylitindilaurate;
0.05 Co7.Orant - CAPONS Blacl X50, a chromium-azo dye from BASF; -was coated over aluminum°coa~ted microspheres as in Exaanple 1 to a wet th~.c)ness of about 150 microns (6 mils) and dried as in Example 1 to yield a binder' layer. An additional layer of the same compositeon was coated t~ a wet th~.~~~e~s og about 200 microns (8 mils) to act as ~n adhesive. The construction was then wet 2p lamin~aed to a polyester fabric and dried and cured thereon as in example 3.
Example 5 was the same c~nstruction except the amounts of coupling, anent end ~H75 were 1 and 3.6 p,a~t~; respectively.
~~ Co~t~ar~tive'Example D was a piece of -8b1 ~e~r~reflective Fabric fr~~ (Inita.l~~ Sp~rl~.ite Company which i~ bel.ieved tca c~~eprise a ~~nolayer of aluma.rrum-coated ~icrcasph~res in ~ ur~than~~based binder ~~icerial .
3~ ,the appliques in examples 4 anct 5 and comparative Example D hid ix~~.tiaa3. retroref lective I bric3htn~sses (in epl) ~of about 5'70, 584 P and X71, respectively. The launderabil~ty results tabulated in ~abl~ 1V were ~brained:
5 ~~$'~e ~V
es Ex . 4 ~_x__ 5 Ex~l~
~ 100 x.00 1.00 ~1 72 45 ~0 5~. 5~ 27 ~~ 93/20x163 ~~ ~ '~ ~ ~ ~ '~ ~'~T,tJ~93,0~?8~... .

30 48 45 1.5 ~0 41 39 8 5p 40. 35 3 ~ 6p 38~ ~~ 33 1 ?~ ~~~ X33 2? <1 .,.
80 32 2? <~
~p 31 26 <1 a.p zap 26 22 <1 xam 1~ 6 Frnd om a at've xam a ~~ make Example 6 a binder composition as described in Example ~ saes coated over a layer of aluminum-coated ~u.icros~aheres to a wet thickness of about 2~p microns (8 pails) and left at room temperature for 5 minutes to permit some ~f the solvent to evaporate, leaving the surface s~xnewhat tacky. The construction w~~ then immediately la~ainated to a 2p ~oly~s~ter fabric as described ire B~ample 1 and dried as in Example ~.
lea C~~nparative Example E, a binder compositian c~m~~isiang ~~,nt Comoon~nt ~5 ~0~ Binder material - 3205 weig&~t percent.
solids solution in methyl ethyl ketone of th~rnaos~tting phen~lic resin (formaldehyde phenol cdnd~snsat~, r~itri~.e rubber, and .
plastici~er (dic~ctyl.phthalate~ in 5:3.3:x.
3~ Freight ratio;
10 8 Cowling agent - I~3I4N CBTDEX189, a gamma- x~ercaptopropyltri~aethoxysilane;
0 ~ 5 carlbon black dispersi~an; end ~:0 titanium dioxa.de di~p~rsi~n;
35 was coated wex ~ l:ayer of alumintan~--~s~~~ed microspheres at a ~ae't thickness of ab~ut 1?5 mid~ons (? mils) and th~x~ dried and cia.red at 66°C (~.5p°F~ fsa~ ~.p minutes then, at 93°C (2p0°F) for 5 minutes ~o ~ie:ld the b5.nder Dyer.

...,,y~ 93/204b3 _1?_ 1~n adhesive comprising loo parts of a EoSTIIC~z"~
7660, 3o weight percent solution in methyl ethyl ketone of polyester dial from Emhart Corporation, and 4 parts of BOSCODUIt~ No. 22, a 66 weight percent solids solution of polyisocyanate from Emhart Corporation was coated over the binder layer to a wet thickness of about 225 microns {9 milsj: The applique was then .
laminated to a piece of hRIMALUX~ Fabric, an 80/20 blend of polyester and combed cotton, basis weight of 3 to ~unces/yard2 (102 g/m2~ from Springs Industries, Inc., and the canst~uction dried and cured at 66°C (15o°F) for 5 minutes and 1o4°C (220°F) for to minutes.
~h~ samples of appliques in Examples 4 and 6 and Comparative Example E used here had initial retroreflective brightnesses (in cpl) of about 587, 591, and 579, respectively. The variation in initial brightness between the Example 4 sample used here and that used above is within the variation routinely abservea in this type of product. The cleaning agents used were 180 gra~as ~of POLYSOL~, a cleaning cancentrate containing petroleum distillates and surfactant from Atochem~ C~mpany, and 180 grams of ULTR~rSIL~. T~~e launderability results tabulated in Table V ~rere 'obtained:
Tab a V ' ' yes ~. 4 x. 6 x. E

'S 80 ?0 1d 58 51 37 1~ 49' ~8 17 20 42 ~0 6 25 ~g 28 2 ~0 35 25 <1 35 34 24 <1 c~ 27 20 <1 P~,°T/US93/0078 ~V~ 93/20~t63 ~ ~ ~ ~ ~ ~ , , r1.8-~Exaanule 7 An applique was made as described in Example 1 except after formation of the binder layer the second layer of material used as an adhesive layer was not applied. instead, a layer of thermoplastic .
polyurethane film was appli~d~ to the binder layer to yield an adhesive layer: ~ .
The resultant retror~flective applique was applied to a polyester/cotton fabric (55/35 blend) and heat laminated at 190°C (3'~5°F).for 10 seconds in a HTX
HT-400 Laminator Tl~e applie~ue had an initial retroref lective brightness of about 524 cpl. The cleaning agents used were 30 grams ~f FACTQR~ Detergent and s~ grams of 'ULTRASIL~. ~Che launderability results tabulated in Table VI were obtained:
Table ~tI
C c ' s ~x~7 p 10 ~D
ao ' S ~2 ~~ ~~
15 ' 9~ 4 ~o '25 Various modifications and alterations of. this iwention'~ill become apparent to those skilled in the art without departing from the sc~pe and spirit of this invention.

Claims (13)

CLAIMS:
1. A retroreflective applique wherein the applique comprises a monolayer of retroreflective elements partially embedded in and protruding from the front surface of a binder layer and said binder layer comprises a flexible polymer having active hydrogen functionalities and one or more isocyanate-functional silane coupling agents.
2. The applique of claim 1, wherein said binder layer comprises at least one polymer selected from polyisocyanate-cured polyester, one component polyurethane, and two component polyurethane.
3. The applique of claim 1, wherein said coupling agent is gamma-isocyanatopropyltriethoxysilane.
4. The applique of any one of claims 1 to 3, wherein said binder layer comprises between about 0.1 and about 10 weight percent of said coupling agent.
5. The applique of any one of claims 1 to 3, wherein said binder layer comprises between about 0.1 and about 7 weight percent of said coupling agent.
6. The applique of any one of claims 1 to 3, wherein said binder layer comprises between about 0.5 and about 4 weight percent of said coupling agent.
7. The applique of any one of claims 1 to 6, wherein said binder layer comprises at least one of a filler, a colorant, a stabilizer, a flame retardant, and a flow modifier.
8. The applique of any one of claims 1 to 7, wherein said binder layer is between about 50 and about 250 microns thick.
9. The applique of any one of claims 1 to 7, wherein said binder layer is between about 75 and about 100 microns thick.
10. The applique of any one of claims 1 to 9, wherein the applique comprises a piece of fabric which is secured to the back of said binder layer.
11. The applique of any one of claims 1 to 10, wherein the applique comprises a layer of adhesive on the rear surface of said binder layer and said adhesive is selected from an activated adhesive and a pressure-sensitive adhesive.
12. The applique of any one of claims 1 to 11, wherein said retroreflective elements comprise microspheres with hemispheric reflectors thereon and said reflectors comprise one of vapor-coated aluminum and dielectric vapor coats.
13. An article of clothing with an applique of any one of claims 1 to 13 attached thereto.
CA 2129983 1992-04-01 1993-01-26 Launderable retroreflective applique with improved retention of retroreflective elements Expired - Lifetime CA2129983C (en)

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US07/862,345 US5200262A (en) 1992-04-01 1992-04-01 Launderable retroreflective applique with improved retention of retroreflective elements
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Also Published As

Publication number Publication date
JPH07505726A (en) 1995-06-22
ES2108262T3 (en) 1997-12-16
DE69314945T2 (en) 1998-03-26
EP0634022A1 (en) 1995-01-18
CA2129983A1 (en) 1993-10-14
WO1993020463A1 (en) 1993-10-14
KR950701079A (en) 1995-02-20
DE69314945D1 (en) 1997-12-04
JP3391452B2 (en) 2003-03-31
EP0634022B1 (en) 1997-10-29
US5200262A (en) 1993-04-06

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