DE2003793A1 - Reflective fabric and transfer foil - Google Patents

Description

M 2765

PATENT LAWYERS

DMn _n . IiAVS-RUSCHKE
■ ÖipJ.-lnj. H; Ji42 AGULAR- ■

Β £ .-; ΐ "ί-; · ί; 33 ÄUBU «t« -Vikioj Jä-Slraii f β

Minnesota Mining and Manufacturing Company »Saint Paul, Minnesota 55101 (VeSt.v.A.) Reflective fabric and transfer film

The invention relates to colored * reflex-reflecting structures, in particular reflex-reflecting fabrics and Transfer slides, being a monolayer of small glass beads or microspheres are embedded in a binder layer, which contains a reflective pigment,

fieflex-reflective transfer foils are used in America kanigeheh patent specification Hr * 3 172 942 (Berg) νοώ March 9, 1965 disclosed. Hereafter the embedded hemispherical rope the pearls with a reflective coating aue silver, aluminum or another reflective metal, e.g. by vapor deposition, or the reflective means for the Flax pearls are obtained using a · reflective pigment · containing a pearl binder ·, such as · pigment » fleoktn au · Aluuiniuni, copper, or au · another reflective metal, od »r« in reflective ·· primary pigment, such as

ORiOiNALiNSPECTED

! Egg dioxide. Are metal coverings or Metal flakes are used, this has a silvery or a matt gray metallic appearance in daylight, however brilliantly reflective when viewed at night. If colored pigments, such as titanium dioxide, are used, the reflex reflectivity is significantly reduced, and the coloring is different from white or has a yellowish tinge.

Another commercially successful reflex-reflecting structure is disclosed in the American patent specification Hr · 2 567 233 (Palmquist et al.) Of 11 · Sept · 1951, in which both silver-coated and differently colored reflex-reflecting fabrics are described. At JSaeht, these fabrics are also brilliantly reflective and show good flexibility within a wide temperature range. Furthermore, the quality of these fabrics is not impaired during washing or cleaning, but they have the same defects as the above-mentioned transfer foils, since they either look silver-gray in daylight, or the intensity or brilliance of the coloration is lacking. Although a white fabric for a long time. When time is desired, the "whitest ^M fabric will look silver gray in daylight, and blue fabrics will not be as blue as is desired."

Attempts were also made to solve the problem su, a white to produce reflex-reflective fabrics or to increase the color intensity of dyed reflex-reflective fabrics, and some of these products have recently been marketed internationally.

One of these white fabrics probably has a clear, placed Yiny! Binder or guami binder (without a reflective coating of SiOg) together with glass beads with an index of 1.9% where binder is applied to a white fabric. You färbintentität or as "Austthen dietet Erstugnitiei istgut and ebenee dit Biegeamkeit or grip) but dit resilience this Woven · leg Waeohen tdtr oh em laugh fie in strength instructive low" umd tbentt tind dit reflex reflexitnsfähigkeitta for tin white · Gtwtbt \ " Ehr iohwaeh, ie · at a Mtiiuag with sanding of known people using a photometer ·, webei for tin ■ oil marriage ·

009832/1363 _{0B (ßiNAL} , nspected

Tissue values of approximately 4.5 can be achieved at best.

Another recently launched. , reflex-reflective fabric, which has essentially the same structure as the aforementioned white .Gewebe, but whose binder layer is _{pigmented with IiO 2} , the resistance to washing and dry cleaning was improved by using a different binding material, such as from this it can be seen that the white of this: tissue is not as intense as the white of the above-mentioned tissue, so that the tissue has a yellowish sheen. Photometer measurements for this white material showed values of the order of 7

In contrast; for this purpose, the invention provides colored 'or white f reflective fabric that is extremely resistant are against washing or dry cleaning, have an extremely good color intensity or color and are also extremely reflective, i.e. the values displayed in photometer measurements for white tissues are 15 to 20 and more.

The photometer display values mentioned in the present application are the reflection intensities the various products measured by a photometer that is close to the beam of incident light is arranged, the angle of divergence between the light source and the photometer is one third of an arc degree »| where the divergence angle denotes the angle which is formed by straight lines connecting the light source with the reflective area and this with the photometer.

Unless otherwise stated, the reflection intensities were measured at an angle of incidence of 5 °, the angle of incidence being that angle that of the light source straight line connecting with the reflective district and one perpendicular to the reflective area straight line is included. The photometer used was made by < . from Photovolt Corporation, New York, Model 20 ,. based.

009832/1363

■ - 4 -

The invention provides reflex-reflecting structures which consist of several layers, the outer layer consisting of a monochromatic glass pearl, the diameter of which is in the range from 25 to 250 microns, and which have a refractive index of at least 1.8. Approximately half of these glass beads are embedded in a translucent binder containing specularly reflective pigment particle cores * the largest dimensions of which are in the range of 8 to 25 microns, whereby it is sufficient if the pigment particle cores are in tangential contact with and with the underside of the glass beads form reflective elements. The translucent binder can contain sufficient IiO ₂ , or other white-appearing agents, if desired. The W translucent binder may alternatively or additionally also more! Contain dyes that give the outer layer a colored appearance (eg, B, blue or red), or a fluorescent pigment. Behind the binder layer, further coloring or opaque layers can be provided, which at the same time serve as adhesive layers, or different types of adhesive layers known per se can be provided. If this adhesive layer is self-adhesive, a removable cover film with low adhesion can be provided.

The invention will now be described in detail. In the accompanying drawings is the

P üg.i a cross section through a currently preferred embodiment a reflex-reflecting structure according to the Invention, whereby glass microspheres briefly approximately rest half embedded in a thermoplastic base layer on a base,

Pig.2 is a cross-section through a structure according to the invention after carrying out a further production stage, whereby the structure according to the? ig.1 with a pigaent cores containing translucent binder vergehe * was · »pigmented on one · thermoplastic adhesive layer was applied,

009832/1363

ORIGINAL INSPECTED

Fig. 3 is a cross-section through another embodiment, the similar in structure to Pig.2, but with an additional adhesive layer on top of the pigmented one thermoplastic adhesive layer is provided *

FIG. 4 shows a cross section through a reflex-reflecting fabric according to the invention, the one shown in FIG Material was bonded to a piece of tissue with the application of heat, the temporary pad and the backing of which has been peeled off, around the portion of the glass microspheres on the side facing away from the tissue to expose

Fig. 5 shows a cross-sectional representation of a part les of the translucent pigment cores containing Binder, which is about half of an egg & er glass microsphere surrounds, creating a reflex-reflecting element,

Pig.6 a cross section through a transfer film according to the Invention, wherein the glass microspheres half in a dry, peelable base naoh the Fig.1 are embedded, on which a pigment cores containing reflective Layer as well as an adhesive pushes applied is that of an embossed, and a low bond strength having peelable film is protected, and

Jig.7 a sar position drawn as a cross-section of an an- I their execution form of a transfer film according to the Invention which corresponds to the embodiment according to FIG. 6 is the same except that, instead of the KIebeschul according to FIG. 6, a different glue line is provided became*

The ligurtn 1-4 show a support 10 made of a dimen- Bunge default 11 stable sheet-like material having a thermoplastic Β · β chiohtung 12 dl "" ine Mono "chicht au» Glaeper- len H carries approximately to half in the layer 12 eint- bttttt »lad. To embed τοπ Glatptrlen in dtn tr ookentn, • b'zlthbartn support 10 könntn vtnohitdtne at iich known · Terfaürtn anftwtndtt wtrdtn, sB the amerikanieohtn in dtr

009332/1363 . ^ _{0RialNAL IN8PECTE0}

Procedures described in U.S. Patent No. 3,172,942. On the exposed Part of the glass microspheres is applied a reflective layer 16, which consists of pigment cores in a translucent There is binding material. An adhesive layer 18 is then applied to the reflective layer. These Layer can be made of a thermoplastic or a thermoset Adhesive or a self-adhesive material, if desired. The adhesive layer is usually mixed with a pigment material that has the color of the the reflective coating 16 containing the pigment cores is reinforced or supplemented.

In the other embodiment shown in FIG the adhesive coating 18 is replaced by an additional adhesive coating 20 added This additional adhesive coating is used if a particularly strong connection with the fabric or with another surface is required.

According to FIG. 4, the adhesive side of the sheet-like material according to FIG. 2 has been brought into contact with a fabric 22 and connected to this with the application of heat and pressure. After this, the carrier 10 is removed from the top of the glass beads peeled off, exposing them and creating a reflex-reflecting fabric (s). This tissue can then to be supplied to manufacturers who produce clothing items from the fabric make, or cut out the strips or badges of rank from the reflective fabric and put on sewing on or inserting into an item of clothing

The Tig 5 shows, in a partially schematic representation, a single inner element according to FIG. 4. The glass beads 14 used in practicing the invention are said to be about 25 to 250 microns in diameter. If the permanent size of the glass beads is below 25 microns, the ability to reflect is significantly reduced. If the average srOIt of the glass beads exceeds the value of 250 microns Weseatlioh, then the flexibility and the grip of the resulting fabric is significantly impaired, and £ ** Gkwebe takes on an unpleasant appearance. Glass beads with a size tob

0 9 8 3 2/1363 _{OR (QtNAL msPBCTm}

■■■■■. : 7- '■'. - "'

50 to 90 microns are therefore preferable. The reflective covering 16 consists of a flexible, translucent binder 17 and from flakes of a mother-of-pearl-like pigment are known per se. In particular, can synthetic pearlescent pigments now from different ■ Manufacturers. Such pigment particles come in various qualities and in carefully controlled size ranges are available, with the largest surface dimension from about 3 to at least 40 microns and the thickness from 20 to 400 microns Millimicrons.

When carrying out the invention, a specularly reflective pearlescent pigment in the size range of ^ j 8 to 25 microns and preferably in the range of chosen about 40 to 200 millimicrons. Those pigments whose largest dimensions are in the range of 10 to 25 microns, are of particular utility, while those pigments ranging in dimensions from 16 to 24 microns are particular preferable*

Mother-of-pearl-like pigments of the selected size range seek to orient themselves in such a way that their flat sides run preferably with partial contact tangential to the coated part of the glass microspheres. With this orientation, there is a good Beflex reflection. If the diameter of the mother-of-pearl pigment particles is less than approximately 10 microns, the tendency is less that the pigment particles orientate themselves in the manner described and come into contact with the glass microspheres, so that the pigment particles act as less deflectors for the incident light rays are effective. If the average size of the pigment particles is below 3 microns, then it is not the main surfaces but rather their edges that lie on the surface of the glass microspheres, so that the light is more strongly dispersed and no satisfactory reflection occurs.

The 3? Ig «6 shows a reflex-reflecting transmission film 24 "which is essentially the one shown in FIG. 2

009832/1363 \

INSPECTED

Composition has except that over the adhesive layer 18 a peelable cover film 26 gate, which the adhesive layer 18 in front of during storage or transport protects against contamination by attaching it to a surface. The cover sheet 26 also serves as a protection when the transfer film is cut to the desired 3-shape.

? The ig 3 * 7 shows another embodiment of a transfer film, in particular, the housewives and ^those: to be used, which have no way to control lamination> press and temperatures. In this embodiment, part of the thickness of the adhesive layer 18 is replaced

by a layer of a thermoplastic adhesive, the jp at fusion temperatures a lower melting point and a Has lower viscosity, so it will be easier for housewives to film it with a fabric or garment using an iron to connect.

The translucent binder chosen must be relatively colorless and resistant to washing and ! some chemicals used, have a relatively good external durability, can be folded without to tear up or to form hoists »and a strong connection

'Have with the glass beads, so that these when rubbing or : Do not scrape off the surface.

The binders can thermosetting W "be plastic either thermoplastic or as examples of resins which can be used as a light-transmissive binder, its led some akrylisohe resins and some alkyd, polyurethane and. 'Ipoxidharze.

A material which is particularly preferable as a translucent binder consists of a composition based on a thermoplastic polyurethane resin to which approximately the same amount of a vinyl chloride / vinyl acetate copolymer resin is added and a small amount of an epoxy resin. holds. If this composition is a binder, dae _; is still described in the following examples, establishes a firm connection with the glass beads, is within

009832/1363

ORIGINAL INSPECTED

flexible and resistant over a fairly wide temperature range against the solvents commonly used in washing and dry cleaning.

Various translucent pigments or dyes or a primary pigment such as TiO ₂ can be added to color the binder layer. One of the difficulties in making a white, reflective fabric using TiO ₀ is that the make coat

so
must be added a large amount of TiO ₂ to achieve a good coloration and a good reflex reflection, that the ability to produce a good connection with the glass beads, is impaired, so that the fabrics produced exhibit no ~ M durability and abrasion resistance and wear out during washing and dry cleaning. According to the invention the use of TiO ₂ in the binder layer is for the production of a white fabric is not required, although a relatively small amount of TiO ₂ can be used, d _o h _# not more than weight, $ 20 on the basis of a solid resin binder, as a pearlescent pigment of a certain size is used to reflect the incident light rays

In order to produce an intensely blue, green, red etc. colored fabric, the binding agent becomes the same color when it is ground translucent or translucent pigment added. | normally the mother-of-pearl pigment is then added, and this solution is used as a reflective binder layer.

In order to promote the coloring of the binder layer, a liohtundurohliform colored base or adhesive layer is applied to the.

In the following examples, the production of white and different colored tissues described, and it will • in b «iondtrs satisfactory ·· liohtdurohlä ·» ig ·· binder resin »yet * a disclosed, where all · amounts are given by weight, provided nothing else «is specified

0 0 9832/1 363 originally inspected

Example I.

A white, reflective fabric was made in the following manner: Glass beads with a breadth of 1.9 and between 50 and 75 microns in diameter were heated into a polyethylene coated Paper embedded approximately up to the middle, that is, embedded in a hemispherical shape. The exposed part of the glass bead layer was then coated with the following resinous reflective layer to a wet thickness of approximately 150 microns »

Parts by weight

highly crystalline polyurethane resin

(Estane 5740 I 130 from B.P. Goodrich) 23.5

a copolymer of weighted 86-13 vinyl chloride-vinyl acetate resin with 1ji interpolymerized malic acid ( ¹¹ VMOH ”resin from Union Carbide) 20.0

Methyl ethyl ketone 106.5 Epoxy resin (Shell Epon 828) 0.75 Dime thyIformamid 75.0 Mother of pearl pigment paste (XVT Paerleecent Paste from Mearl Corp.) 100.0

The polyurethane resin had the following physical properties j

specific weight 1.20

Shore durometer hardness A 95 Tensile strength 9800 Module at 3005 <-iger expansion (pei) 930

Elongation 730

The epoxy resin is made from epichlorohydrin and bisphenol-A and has an epoxy equivalent weight of 180-195 and a viscosity of 10,000 to 16,000 ope. Di · pigment paste • Contains 35 * lead carbonate plates or crystals, their main subscription 14-22 microns and in duration approximately Micron is the amount of platelets that are suspended in a polyvinyl chloride methyl isobutyl ketone solution.

This · reflective · Sohioht was 15 minutes getrooknet kei sound a temperature 80 ⁰ O. On 4i «s« reflective

009832/1363

* ORIGINAL INSPECTED.

Layer becomes an adhesive layer by means of a doctor blade a wet thickness of approximately 405 microns with the the following resinous solution applied «

Parts by weight

Toluene. '15.50.

Methyl ethyl ketone 29.55

Dioctyl phthalate "15.00

Epoxy resin stabilizer (Ferro 900) 0.25

Resin stabilizer of the bayium / cadmium salt of synthetic carboxyl

acid with organic inhibitor

(Ferro 1203). ~ 0.25

Cadmium resin stabilizer / organic inhibitor (Ferro 203): 0.35

.87 »13 (by weight)

Vinyl chloride i vinyl acetate resin. ■■ .- ■ «.

(VYHH-Union Carbide) x -22.50

Polyurethane resin (Estane 5740 X 130) '8.30

8.30 /

This layer was cured for 20 minutes at a temperature of 60 ^{0 O ·}

After the adhesive layer had cured, the coated side of the material was covered with a 225 g twill fabric consisting of 65 $ cotton and 35 $ polyester. This assembly was carried out at a temperature of 155 ^° C. and a pressure of 1.4 kg / cm carried out. The polyethylene paper was then peeled off in order to expose the area covered with the glass beads, which is reflective. When measured with a photometer, the hetroreflective efficiency PlT «18.4. Ü & b fabric had good flexibility and a "pure * ¹ white appearance * The material withstood repeated folding and washes.

B e i a pi e 1 II

The production of a blue fabric is described below. Am used as a base, coated with polyethylene Paper was coated with the same glass beads as • described in example I. This glass beaded material was then coated with the following resin solution, the

009832/1303

when wet, had a thickness of approximately 155 microns.

Parts by weight

Polyurethane resin, as in Example I 23 »5

the 86 «13 vinyl chloride

Vinyl acetate resin as in Example I 20.0,

Methyl ethyl ketone 106.5

Epoxy resin as in Example I 0.75

Dimethylformamide 75.0

Phthalocyanine blue pigment 2.0

Pearlescent pigment paste, like

according to example I 100.0

The phthalocyanine blue pigment was in a ball mill to a fineness of 7 or higher (Hegman reading) in a slurry with all ingredients except of the mother-of-pearl pigment. The mother-of-pearl pigment was added while stirring shortly before application

This reflecting layer was dried for 15 minutes at a! Temperature of 8O ⁰ C.

An opaque colored base layer was then applied using a bakel, which when wet had a thickness of approximately 105 microns and consisted of the following composition!
* Important parts

Polyurethane resin, as in Example I 23.5

the 86x13 vinyl chloride

Vinyl acetate resin as in Example I 20.0

Methyl ethyl ketone 106.5

Epoxy resin as in Example I 0.75

Phthalocyanine blue pigment 5.0

IiO ₂ 7.0

This mass was applied directly to the reflective covering and dried in the same way »

As described in Example I, an adhesive layer was applied with the same composition and cured at a temperature of 60 ⁰ O (20 minutes) and KLt dem

009832/1363

Fabric according to Example I covered. The retroreflective and with « The layer covered with glass beads was made by peeling off the polyethylene paper exposed. The reflection efficiency was PV »15.2. The color was light blue and more saturated than at the older blue reflective fabrics.

Be is ρ 1 el III

= ■ .- ■■ ■. . · - ■, ■ - j '

In the example below, the production of a orange fluorescent reflective fabric. The beaded polyethylene paper was made reflective as in the previous two examples Apply an eeflektorschicht, which in the wet state a Thick clay approximately 205 microns and having the following composition

Parts by weight

Polyurethane resin, as in Example I 23.5

the 86 ti3 vinyl chloride

Vinyl acetate resin as in Example I 20.0

Methyl ethyl ketone. 106.6

Epoxy resin, as in Example I 0.75

Light orange pigment (Switzer T-15) 40.0

Mother-of-pearl pigment, as in Example I 50.0

Dae orange pigment was measured by a ball mill prior to the addition of the other ingredients into ground in the vinyl resin Methyläthylketonlösung * The mass was then cured at a! Temperature of 80 ⁰ C for 15 minutes · By means of a doctor blade then wurdt an opaque colored base layer having a thickness of about 155 microns applied to the reflective surface when wet. Isschioht the liohtundurchlässige colored Bae had the following composition aufι

Weight parts

Polyurethane hairs as in Example I - 23.5

Vinylharxkopolyiier, as in Example I 20.0

Metyläthylfcetoii 106.5

Epoxy resin, as in example I> 0.75

20.0

The grinding was carried out using an Oowles dissolver.

_{The relatively large amount of TiO 2} used in this opaque colored coating compared to the earlier examples resulted in a more intense or brighter looking fluorescent reflective layer.

The opaque and colored layer was then applied an adhesive layer as described in Example I, and the film was then applied to the fabric under the same conditions connected as described in Example I. The glass beads were made by peeling off the polyethylene coated Paper exposed. The eetroreflection efficiency is

™ carried PV = * 3.5

Example IV

This example is making a white reflective reflector Broadcast film, which is particularly useful for individual consumers, e.g. for housewives.

Glass beads with a Breoh number of 1.9 and a diameter from about 45 to 75 microns were heat deposited in a polyethylene layer on paper to Center embedded as described in the examples previously described · The exposed portion of the glass bead was then with the following translucent and reflective resin composition coated to a thickness of approximately 125 microns when wet

Parts by weight

Polyurethane resin, as in Example I 23.5 D

the 86113 vinyl haracopolymer, -;

as in example I 20.0,

Methyl ethyl ketone 106.5

Epoxy resin, as in Example IO ₁ 75

Dimethylformamide 75.0

Mother-of-pearl pigna

(TOQ Pearl Pigment from Kopper · 0o.) 38.5

009832/1363

OR'GiNAL INSPECTED "

■ ·. '■■ ■:. - 15 - ■ ·

The mother-of-pearl pigment composition used in this example consisted of lead carbonate flakes, the largest dimensions of which were 16-20 microns and an average of about 18 microns * A paste of polyvinyl chloride resin dissolved in methyl isobutyl ketone contained $ 60 by weight pigment.

This reflective layer was dried at a temperature of approximately 107 ° C (for 4 minutes). - ■ ^{x applied} by means of a bakel to the / reflective layer an opaque adhesive layer with a thickness of about 250 microns in the wet state, using the same adhesive layer as in Example I was used.

This layer was cured for 5 minutes at a temperature - M of approximately 93 ^{° C.} A third layer of adhesive material similar to the second layer, but _{containing no TiO 2} , was applied to a thickness of approximately 125 microns in the wet state and cured for 4 minutes at a temperature of 93 ° 0 and embossed with a 50 micron thick Polyethylene cover film connected, which is removable. This product can be supplied in bulbs or strips and can also be applied to fabric or clothing by means of a common iron. The material is cut to the desired size, after which the polyethylene cover film is peeled off and the exposed side is placed at the desired location on the base. An iron heated to approximately 85 to 160 ^° C. is used to press the laminate | used on the tissue, which takes a time of 30 to 60 seconds. After cooling, the polyethylene-coated paper carrier covering the upper part of the glass beads is peeled off, exposing the white reflective glass bead layer.

Was Although in the above examples, the currently early Y _e rfahren for producing reflex-reflecting Übertragungefilcen and Gewebtn described, so can be applied, however, other Ahren · tert. For example, one or more layers can be applied one after the other to the cover film 26 or the fabric, and the glass beads can

00 983 2/136 3

- 16 -

be scattered on the reflective layer when this is still damp * Please note that »the reflective coating still has sufficient solvent at the time of application should contain, so that the mother-of-pearl pigment can calibrate so that a substantial number of the platelets can form a reflective layer which makes tangential contact with the embedded parts of the glass beads can.

As is known per se, in the case of an air-glass bead interface the most effective reflex reflection obtained with glass beads, the refractive index of which is approximately 1.90 to 1.93. Will the surface of the glass beads is wetted with water, then the glass beads have a refractive index τοη approximately 2.5, at which the most effective reflex reflection occurs. In the manufacture of the products according to the invention, the use of a Mixture τοη glass beads with a refractive index τοη 1.9 and 2.5 be desirable if the product is to be used on items of clothing, e.g. on raincoats

Claims

009832/1363

Claims (1)

- 17 - P a tent a η s ρ r ü e h e Eeflex reflective structure with a mono layer Glass beads whose size ranges from 25 to 250 microns and whose refractive index is at least 1.8, which Glass beads about halfway into an essentially translucent binder layer embedded and firmly connected to this, with the embedded Cup-shaped reflecting plates around the glass beads are arranged, characterized »that the Binder consists of specular reflective mother-of-pearl pigment platelets contains, the largest dimensions of which are approximately 8 to 25 microns * 2 «Beflex-reflecting structure according to claim 1, characterized characterized in that the largest dimension of the mother-of-pearl pigment particles averages in the range of 16 to 24 microns. 5 »Seflex-reflective structure according to claim 2, characterized characterized in that the translucent binder consists of a mixture of approximately equal amounts of a highly crystalline Polyurethane resinsea and a vinyl resinβ which consists of a copolymer and as a main part Polyvinyl chloride and a small amount of polyvinyl acetate contains ». 4. Structure according to Anipruoh 1, 2 or 3 _f daduroh. marked, that * over the middle surface layer a ", thermoplaatieohei lichtundurohläeeig" pid colored layer is arranged, 5. S trijktur na oil tin * ia d * r Yö.r * ttliend «n JLßfprtlöht, thereby gekeHÄe * iohn # t, dmee di «structure with tinam Saw * t <e iuiammen 0Q98 32/136 Blank page