DE1902632A1 - Self-adhesive decals - Google Patents

Description

m, §§umL ^^ ^zo · ^Jan · ¹⁹⁶⁹

Lo / H - J 1000

f * # fβ

KATTHSY Λ CO. LZNISKD

78, Hatten Garden
London, JS. C. 1 /

"Adhesive decals ¹¹

PRIORITY: Longland from January 19, 1966 No. 3062/68

The invention relates to self-adhesive adhesive stickers for attachment of decorative and other patterns on, among other things, heat-resistant substrates, e.g. pottery products, Glass, metal or the like

Self-adhesive decals are well known but suffer them of certain shortcomings. Generally such decals contain sensitive, low tack adhesives, which require 'substantial pressure' tac liability

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BAD ORIOINAL

To effect a heat-resistant pad on the receiving surface, these decals may not work satisfactorily on irregular surfaces or surfaces with complex ones Curvatures are applied.

It is not the aim of the invention to create “self-retaining decals for the application of decorative and other patterns on heat-resistant substrates, which are based on these substrates can be applied under slight pressure and which are sufficiently flexible to be able to work on documents with irregular To glue surfaces or complex curvatures

According to the invention, a self-adhesive decal for applying a pattern to a base comprises a fiückachioht » a release liner on at least a portion of each surface of the backing layer, one applied to a release liner and one or more Schioh1 ^^ onI) ruok (colors) to aniQeneerung "use" embracing pattern layer and the pressure-sensitive adhesive layer B having high tack, which is applied to the aforesaid Cough layer applied iet.

The separation layers, one of which is applied to each surface of the backing layer, can have differing release properties, and the. Separation layers are preferably made of polyeiloxane material, polyBiloxane material has the general formula (R ₂ SiO) _n , where η is a positive integer and R in the simplest foil is a methyl group Alkyl groups can be replaced · Furthermore, monomers

according to the used

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modified to form a crosslinked eu molecule, whereby, a two-dimensional or three-dimensional polymer is formed.

The separation properties of a separating layer depend mainly on two factors, namely the composition of the separating layer - a chemical factor - and the relative smoothness (or structure) of the surfaces of the gap layer to which the separating layer is applied - a mechanical factor »FUr a separating layer, which has a certain ohemical composition, therefore the peeling properties 'depend' on the mechanical factor - let for example the extent of the adhesion or the mechanical bond between a relatively smooth surface and a film, a paint or an adhesive is relatively small If, on the other hand, the same film, paint or a binding agent is applied to a less smooth surface, for example a coarse-grained surface, a relatively good mechanical bond results.

The thickness of the release liner is usually such that the Contour line or the machining of the surface of the separating layer from the machining or contour line of the back to the near g ·· * follows, or is reflected in this »So is in the case that a separating layer on a back layer with a smooth Surface is applied, the surface of the separating layer is also smooth and, in the event that the backing layer, rough or has a coarse-grained surface, the surface of the separating layer likewise has a rough or coarse-grained surface. This concept, that the machining or the contour line of the surface of the rear layer is in the machining or height

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line of the release liner, is used in the invention to facilitate the transfer of stacking of decals and the like so-called "blocking *", i.e. sticking adjacent decals in a stack next to each other, lower down ·.

According to a feature of the invention, the surface of the back layer, which has a release layer, the protective layer and the layer of pressure-sensitive adhesive bit, is smoother than the surface of the back layer, which carries a single release layer. Assuming that the decals are in In a stack with the layers of the pressure-sensitive adhesive with high tack (which is usually the case), the separating layer or individual separating layer mentioned above has a relatively lower contact area compared to the layer of pressure-sensitive adhesive with high tack, d 'h · dee Absiehbildes next in the stack, whereby easy detachment of the Absiehbilder of the stack is possible Se ₀ has been found that a RUokschicht with a Scbälfestigkeit of not higher than 1.2 g / om (3 g / linear inch) is suitable for the page, which appears a separating layer, pattern and adhesive "middle layer with high adhesive pressure sensitivity, and that a peel strength no higher than 6 g / oa (15 g / linear inch) is suitable for the opposite surface which carries the individual release layer _{or the like}

The back layer can be in sheet or strip form and comprise one or more sole / s of a flexible material. Suitable materials include:

1 · «in PolytheneCPoljratshylea) from lower to

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Density, for example 0.92-0.935 g / δ >>³; 2 " a paper / polythene-Sohiohtetoff;

5. a polythene / paper / polythene laminate; 4. polyethylene or polyethylene / paper laminates; 5β paper, and

6. a flexible film material

Sine combination RUckeohioht-Xrenneohioht which was particularly suitable were, is brought from Inveresk Paper Company of London, England, in the trade and comprises a layer of polyethylene, which iat coated on each of its surfaces with a layer eines'Polyalloxaxmaterials ₀

The pattern layer can be applied to the backing layer with the aid of a screen, cliché, letterpress, bryoffset, flexographic printing process or a lithography process, or any combination thereof. The adhesive layer can be applied as a complete overcoat using any standard surfacing technique, or it can be applied to the decorative. or other surface with a pattern can be bound by printing the adhesive using screen or cliché * or flexographic printing processes.

SAS decal BQ produced can be subject to hitaebeständige or other, for example, cans, bottles, and the like äunatstoff- & aXlohe "B ₉ either automatically or aanuell

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Ill punched out form or from an endless balm, ie with the IlUokschicht or the Pils in the form of a strip or band, are applied. When such a decal is applied, the highly adhesive adhesive layer binds to the non-stick underlay with the decorative or other pattern firmly adhering to the surface that is standing on the floor. Za lalle the use of color with polythene fileen, measured the color layer be selbet sufficiently flexible to the application of the Muaters on surfaces of complex curvature to ermögliohen · The production of Abssiehbildern gemäfi the Srfindung can also sur production vjpn self-adhesive labels used wordene

You can use printing ink for the decorative or other type of pattern be based on a variety of materials, sometimes nitrocellulose and cellulose esters modified Collophonium, alkyd resins, condensates from cyclic ketones, Maleic, amine * and acrylic resins,

Acrylic resins are preferably used, and it is desirable for the color medium to be a plasticizer and surface-active Substances to achieve the desired layer-forming flower properties and give up rejection inheritance "

A typical Farbaaaatz based on an Acrylnarses is:

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pigment 60 * Acrylic resin 14.5 * solvent 22.0 % Plasticizers 1.5 # Surface active substance 2.0 f>

100.0

The coloring material used can, depending on the intended use, consist of a supporting underlay inorganic pigment with a portion of a vitreous Ha » teriais susanzuteetst eein, as the expert from! known 1st, or on the other hand in the foil, that the hit-resistant underlay is not exposed to high temperatures, can be a heat-resistant organic pigment can be added.

For example, a flux or a glass matrix made of lead silicate, lead borosilicate or lead alkali metal silicate with smaller amounts of modifying ozyde and the addition of known, inorganic parboil compounds, such as cobalt aluminate, cobalt silicates, cadmium sulfoselenide or lead antimonate can also be used, provided that organic pigments can also be used together they are light-fast and to sin »least 200 G ⁰ · heat-resistant (for non-ceramic uses) Typical pigments, which have these properties are ι Isoindolinongelb-," orange and -rotfarbstoffe, Bioxazlnviolett-Parbstoffe, Phthalocyanine and -green - Colorants * The following are examples of acrylic resins, solvents, plasticizers and surface-active substances:

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Acrrlharst Methyl methacrylate / Butylme theorylat -Copolymerieat · 2-Ethyl-hexyl-

aorylate and polybutyl-s & ethacrylate

Beter _v such as amyl and butyllaot, arooatieoh "hydrocarbons" for example xylene, alcohols, for example acetone alcohol, glycol ether esters, for example 2-Ethox7äthaBOlaoetatj but other _} well-known solvents, can also be used.

Diootylphthalaty Dibutylphthalate and Butylphthialylbutylglylcolatj however, other well-known plasticizers can also be used.

Surface active substance » .

Om to achieve when printing on Silikonbeechichtungen good film-forming properties, "it iat necessary to impart the Druckmedlua surfactants" Suitable materials proved verifiable stearic acid and its derivatives ,. Olycerin monostearate and stearic acid amide, marketed as Amid HT by An & our Hess Chemioals

Different examples of specific colors and colors with inorganic and organic pigments are below specified:

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wenduiy? for core mixing

t. Cadium red; ceramic dtnail 64.3

Polybutyl methacrylate 14.2

Xylene 8.4

Amyl lactate 3.5

Dioctyl phthalate 1.8

Armid ΗΪ. 1.8

Lead antimony yellow; Jteramiechee. E-mail

2-ethyl-hexyl acrylate

Amyl lactate

Butyl phthalyl butyl glycolate

Stearic acid

Cobalt blue; kepami ^ phes isjnail

Polybutyl methacrylate / methyl methacrylate copolymer

Diacetone alcohol

iibutyl phthalate

Glycine monostearate

1 00.0 % 61.5 i » 16.0 18.8 $ 1.9 1.8 1 00.0 67.3 * 13.5 15.5 "A. 2.0 100.0 *

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4o Irgazin & elb 3 GLT (ßeigy Ltd,) 18.0 pounds Polybutyl methacrylate 36.0 % Xylene 18.0 Jo Amyl lactate 24.0 3ί Dioctyl phthalate 1.0% Asaid HT 3.0 56 100.0% 5 ο Irgassinorange BLT (Geigy Ltd «,} 15.0 36 2-ethyl * h6xylaorylate 40.5 % Amyl lactate 40.5 56 Butyl phthalyl butyl glycolate 1.5% atearic acid 2.5 % 100.0%

6. Irgalite blue BQL (Geigy Ltd.) 10.0

Polybutyl-ethapylate / methyl-aietliacrylate Copolym.erissat 43.5 Dlaoetone alcohol 43.5 Bibutyl pbtbalate 1.0

Olyceriui Boaoetearate 2.0

100.0

Dae appropriate, pressure-sensitive adhesive 1st so it "Beilin burning quietly without passing through a Schmelebereiches burns · For dieeea are basically adhesive to £ based on acrylate! Polymers and Acrjl-vinyl acetate CopQlyiaeriBaten the eeeigaetsten, and it is necessary that the selected Ha · The material is soft-dipped on the inside and permanently sticky is « EXa.

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sches Reeept that gives satisfactory results is:

Acrylic resin $ 22.25

Alcohol 50.0 i>

Athylaeetat 23.15 f>

Hexane 4 * 6 ¥>

100.0 %

Fall using an adhesive with even higher If skill is desired, the following recipe is alternatively suitable net:

Acrylic resin 21.8 ~ 20.5 lbs Sucroee'acetate)

isobutyrate) ² »° * ⁷ » ⁵ ^

Alcohol 49.0 -46.25 *

Ethyl acetate 22.7-21.5 %

Hexane 4 * 5 * 4.25 i>

100 J6 100 %

Examples of suitable and commercially available adhesives are: Adhesive K 7503 (Swift & Co. Ltd.) "Howstik 255 (W ₀ E. Hewlett & Sons Ltd · } and Gelva 263 (Honsaato)" In practice, these substances are made with polymerized and hydrogenated collophonium harsen, collophonium esters, chlorinated diphenyl compounds and sucrose acetate butyrate modified

Examples of modifying substances are: Polypale Resin, Staybelite Ester 3 (Hercules Powder Go «), Aroolor 5460 (Monsanto) and sucrose acetate isobutyrate (Eastuan Kodak Chemicals)

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They modifying substances are added in a proportion of 20 i * to the desired adhesive properties, and Kohäaion Iragerfähigkeit eu reach · Lösungemittel and VerdtinnungB "medium are also the Haftnittellösung sugefUgt to dio desired Fließeigensohaften achieve eu. The solution eau t el and thinner are carefully selected so that they do not attack or penetrate the underlying paint layer. In this regard, alcohols and aliphatic hydrocarbons have proven to be satisfactory and typical examples are: Shell SBF6 »Laokbenein imd aliphatic. Solvents 20/2 and 17/4 (supplied by Carless Capel & Leonard). The solvents that can be used are not exclusively restricted to these types; for example, solutions of hangovers and aliphatic compounds also work satisfactorily.

The following are examples of solutions more pressure sensitive Adhesives listed:

7- Howstik 255 44%

Folypale- ^ Resin 5 > Z-ethyl-n-butyl alcohol 51 %

100 yrs

8 "Gelva 263 40 %

Sucrose acetate isobutyrate 20 % Oarless aliphatic 20/2 40 %

1ΟΟ.? Ί

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9o Swift K 7503 56

Staybelite lister 3 5

Nony! Alcohol

Gelva 263 Staybelite Ester 3 .Butyllaotate gasoline (White spirit)

100 # 46, 5% 4, 5 36 19 0 2 & 30, 0 yrs 100

A decal produced according to the invention can be used for the application of single-layer or multi-layer surfaces of a conductive or insulated or dielectric or semiconducting material or of resistance material or of three or more such layers on a heat-resistant or other base in one work step resistive material _f which included in the print medium 1st "Edelaetallei example, QoId ₉ silver or platinum" or alloys or compounds containing these metals, or include alloys and can then air fired -Be "However, such materials, other metals and their compounds contain , for example molybdenum "which anachliessend in the air or in an inert or reducing atmosphere depending on the material concerned * thereof are fired wad * alloys of molybdenum. ftangan or metals or alloys belonging to the eighth group of the period synthem metals can also be used

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The resistor materials can be made from compounds such as oxides from one of the aforementioned metals alone or alloyed with one or more of the aforementioned metallic elements.

The conductive substances or Wideretandmaterialien may include binders, "which may be silicate-like in nature, for example, lead borosilicate or even Quara" This includes but not the use of other binders _t example from Wiemutoxychlorid and other materials "

Dielectric materials can contain any state-of-the-art substances, for example titanates », such as barium titanate * Other materials Codified dielectric materials, for example, bismuth titanate, can also be used contain such binders, as explained above in the description τοη resistor materials and conductive materials «,

Insulating materials can aase materials with a glaze, for example lead borosilicate, and they are available in two forms, vitrifiable material and all Material "which nucleates and crystallizes when it cools down"

Examples of semiconducting materials are Cadminumaelenide and the sulfides of IXJd, Pb, Zn and mixtures thereof.

The procedure described for the application of decorations and other sextons on heat-resistant * underlays offers a greater advantage over normal working methods because of this »

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that the inventive vegetable decal on the pad without the Use of high pressure to activate the adhesive layer and can also be applied to surfaces that are uneven or have complex curvatures »

Another advantage is that the image according to the invention directly on unglazed bite-size porcelain without the hotweadiness a previous sealing of the pores of the goods old a «primer can be applied ·

lias the application of conductive or insulating or dielectric or semiconducting surfaces or resistance surfaces on heat-sensitive documents concerns »so these are in all *. common on a base in the form of a ceramic body, with * for example a ceramic disc, printed. So it wasn't always possible, because of an even deposit of the printing ink To achieve surface irregularities of the substrate »A according to the invention-produced, self-adhesive decal overcomes this handicap

The decal has the further advantage that a multi-layered surface can be applied in one work step » instead of a series of separate, single-layered Aixftragun & s is required, as is often necessary with direct printing.

As an example, two decals according to the invention are shown in FIG Drawing reproduced

In the drawing the different layers of the decals are marked with lobsters, where 1 is a back layer,

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2 and 5 Poly eiloxan Treim layers, 4 a Muetersöhicht and 5 a pressure sensitive adhesive layer with high tack mean · If the decals according to the invention are used for decorating ceramic, glass-like or other goods the sexton consists of a pictorial representation «) However, as shown earlier, the cough can be a resistance » material, conductivea, semiconducting, dielectric or insulating material sur use in the manufacture of electrical Items include * ».

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Claims (1)

PAIMIAH SAYING: 1 · Self-adhesive decal for applying a pattern on a base, characterized in that there is a layer, a separating layer on at least part of each Surface of the backing layer, one applied to a separating layer and one or more layer (s) of a printing composition, and one layer of a high tack pressure sensitive adhesive applied to the core rail 2o transfer according to claim 1, characterized in that dafl the separating layers have different inherent properties. 3 «picture according to claim. 2, characterized in that the different separation properties τοη dtr r «latiT * n Depend on the smoothness of the surfaces of the rear view. 4 · image according to claim 3 »marked thereby» dafl the surface of the rüoksohioht, which is a separating layer that Hustersohicht and the Sohiaht of the adhesive with high sticky * is relatively smoother than the surface of the backing layer, which only has a separating layer. " Si transfer picture according to one of the preceding tests, characterized in that each separating layer is made from a polysiloxane material " 6ο transfer according to claim 5 » characterized in that the polysiloxane material has the general formula (RgSiO) ^, where R is a methyl group and η is a positive integer« - 17 -909835/1039 7. Decal according to claim 6, characterized in that at least one methyl group is replaced by an alkyl group. 8o transfer according to one of claims 5, 6 or 7, characterized in that the rear layer has one or more layers of a flexible material made of polyethylene, polythene or paper 9, image according to claim β, characterized in that the polythene (polyethylene) has a diet of between 0.92 and 0.935 g / cm o It) 10 »decal according to one of claims 1 to 9, daduroh in that the must erschient one or more Schiob / s includes an ink composition comprising a pigment and a base of nitrocellulose, Celluloseestern, modified rosin, alkyd resins, condensates of cyclic ketones _f maleic , Amine or aryl resins. 11. Transfer according to claim 10, characterized in that the ink composition includes a plasticizer, 12 · Transfer according to claim 11, characterized in that the plasticizer consists of dioctyl phthalate, dibutyl phthalate or butyl phthalyl butyl glycolate » 13 «Decal according to claim 11 or 12, characterized in that that the "ink composition includes a surfactant" - 18 909835/103 9 14o transfer according to claim. 13 »marked there, that the surface active substance consists of stearic acid or its Derivatives »Glycerin monostearate or stearin & ureamide consists of · 15 "decals according to claim 10, characterized in that the thick paint composition 64.3 # cadmium red, ceramic snail» 14.2 # polyhutyl methacrylate, 8.4 % xylene, 9.5 amyl lactate, 1.8 ml uioctyl phthalate and 1, 8 £ stearic acid amide (Annid HX). 16 · Absiehbild, according to claim 10, characterized in that the printing substance composition comprises 61.5 % lead antimony yellow, ceramic enail, 16.0% 2-ethylhexyl acrylate, 18.8% aayl lactate, 1.9 / 5 butylphthalyl butyl glycolate and 1.6% stearic acid · 17 · decal according to claim 10, characterized in that the DruckfarbenzuBaiomensetEung 67.3 £ cobalt blue, ceramic β email, 13.5% Polybutylttethacrylat / lKethylnethaorylat-Copolymerieat, 15.5 $ Siacetonalkohol, 2.0 i »Oibutylphthalat and 1.7% Includes glycerol monostearate. 18 "decal according to claim 10, characterized in that the Druckfarbenzueanmensetzung 18.0 f» Irgazingelb 3 GLT (Geigy Ltd.), 36.0 ^ Polybutylmethaorylat, 18.0 i »xylene, 24.0% Affiyllactat, 1.0 fr Dioctyl phthalate and 3.0> Armid HT includes. 19 · decal according to claim 10, characterized in that the Druoktarbenzuseimaensetzung 15.0 f> Irgazinorange BIS (Geigy Ltd.), 40.5 Ϊ 2-ethylhexyl acetylate, 40.5 $ amyl lactate, 1.5 % . Butyl phthalyl butyl glycolate-.and 2.5 i * stearic acid comprising - 19 - 909835/103 HO "decal according to claim 1 _0} characterized in 'that the Druekferbeniiisairanensetzung 10.0 # Irgalitblau BGL (fiddle: / Ltd.)? _R 43» 5 x> polybutyl methacrylate / methyl methacrylate · Qopolyffierieati 43 _e 5 £ Dieeetonalkohol, 1 _f 0 V "Dlbut, / lphthalate and 2 _f 0? *" Glye 2ift decal. n & oYes a äex * preceding claims, characterized in that _t the pressure-sensitive adhesive with high Klebriglceit an acrylic or vinyl acetate-Acryl'-öopolymerisatbaslB l) esltset _e 22p Ahziehliild according to claim 21 ₁ characterized in that the adhesive 22.25 Ϋ » acrylic resin ^ 50; * alcohol, 23.15 $ ethyl acetate and 4 _f 6 5 & hexane comprises ο 23 decal according to claim 21, characterized in that the adhesive ,, 21.8 j6 - 20.5% acrylic resin, 2.0 - 7.5 acetate Sucroge-# and -isofcutyrat, 49.0 to 46.25 ⁰ A alcohol , 22.7 2.1.5 Ϊ * includes ethyl acetate and 4.5 - 4.25 f ° hexane " 24ο transfer according to claim 2.1, characterized in that the adhesive comprises 44% Howetick 255, 5 5 »polypale resin and 51 f» 2-ethyl-n-butyl alcohol * 25 · decal according to claim 21, characterized in that the adhesive means 40 i »öelva 263, 20 ^ Sucroee acetate isobutyrate, and 40 ⁰ A Carleee comprises aliphatio 20/2 ,, 26c transfer according to claim 21, characterized in that the adhesive 56 JS Swift K 7503 «5 P Staybelitester 3 and - 20 - SAD ORIGINAL 909835/1039 39, "A includes nonyl alcohol. 27 · Transfer according to claim 21, characterized in that the adhesive comprises 46.5 £ Gelva 263, 4.5 1 " Staybelitester 3, 19.0 jS butyl lactate and 30.0 £ White EPLIT", 28 «. Decal according to one of Claims 1 to 14 and 21 to 27, characterized in that the printing inks are renewed a conductive, insulating, dielectric, semiconducting Includes material or a resistance material » 29 «transfer according to claim 28, characterized in that that the conductive material or resistance material is a precious metal, a metal from group VIII of the periodic table or alloys or compositions containing these metals includes o. 20 «transfer according to claim 28, characterized in that that the conductive material or resistance material is a Le * alloy of manganese and molybdenum is 31 ο transfer according to claim 29 or 30, characterized in that the conductive material or resistance material includes a binder made of silicon dioxide, lead borosilicate or bismuth oxychloride _o 32. Transfer according to claim 28, characterized in that that the dielectric material is a titanate 33ο decal according to claim 32, characterized in that let the dielektriüc «« Matioriai BnrlujnfcUntmi or / i ⁰⁴⁰ JU 34 »Transfer according to claim 33» characterized »in that the dielectric material includes a binder made of silicon dioxide or lead borosilicate ₀ 35 ο transfer according to claim 28 ₉ characterized »that the insulating material is a vitrifiable material or a nucleating material that crystallizes when cooled down» 36 ο Transfer according to claim 28, characterized in that the semiconducting material consists of cadmium selenide or the sulfides of cadmium, lead or zinc or mixtures thereof 37β transfer according to claim 10 »characterized» that the printing ink composition comprises: 70 - 59 i> inorganic pigment content, T2 '<= ■ 18 # acrylic «» or methacrylic Homo- or Gopolyraerleate, 15 - 19/5 orge solvent !. 1.5 - 2 # V / calibrators and .1.5 ~ 2 ^ stearic acid or derivative 100 J5 100 f> 38ο transfer according to claim 10 »characterized in that the printing ink composition comprises: 20 7 i> orgo colors»
35 - 45 ^ S acrylic or methaoryl « Homo- or co-polymer! Sat, 40 "45 $> orgo solution agent _for 2 - 1 Ji Weichmaoher and 5-2 $> stearic acid or" derivative TOO? 6 ΓΟΟ BAD ORfGiNAL