DE10361541A1 - Adhesive film for implanting electrical modules in a card body - Google Patents

Abstract

Adhesive film consisting of a blend of a synthetic rubber S1 and a thermoplastic 2, wherein DOLLAR A a) the blend is microphase-separated DOLLAR A b) the blend has at least two softening temperatures, wherein at least one softening temperature is greater than 65 ° C. and less than 125 ° C. DOLLAR A c) a measured according to test method A G 'at 23 ° C of greater than 10 · 7 · Pas DOLLAR A d) has a measured by test method A G' 'at 23 ° C greater than 10 · 6 · Pas has DOLLAR A. e) and a measured according to test method A crossover of less than 125 ° C has DOLLAR A for bonding of electrical modules in smart cards.

Description

The The invention relates to a blend of at least one thermoplastic and a synthetic rubber, this with an Implantierstempel at 150 ° C activated and used for bonding electrical modules with card bodies becomes.

For the implantation of electrical modules in card bodies, a large number of adhesive films or joining methods are already known in the prior art. The aim of these implants is the production of telephone cards, credit cards, parking cards, insurance cards, etc .. Examples of the corresponding bonding methods can be found for example in the patents EP 0 842 995 . EP 1 078 965 and DE 199 48 560 ,

In However, in this area of bonding, the requirements are constantly increasing to the adhesive system. So the glue needs a good adhesion to polycarbonate, on ABS, PVC and PET, but also good adhesion to electrical module. This is usually on epoxy materials, Glued polyesters or polyimide. Previously, cyan-acrylates were used as liquid adhesives used, which have the advantage that optimum wetting of the card body and the electrical chip was achieved. This technology is but dying out because the processes are very slow. The solvent evaporated only slowly from the cavity of the card body, the Syringes for dosing clogged by dehydration at standstill and were also difficult to dose and the liquid adhesive needed as well a certain amount of time to cure. As a result, the quality was the bonding is pretty bad.

Here the hot melt pressure sensitive adhesives are clearly superior to liquid adhesives. Nevertheless, the selection of suitable connections is very good here as well limited, because very high demands are placed on this joining technology. A restriction are the very different materials that need to be glued. By the very different polarities of PC, PVC, PET, ABS, Epoxy and polyimide are impossible to find a single polymer which is the same on all materials good adhesion. A possibility to increase the adhesion on different substrates is the mixture of different Adhesives. But again, the problem is a stable mix to achieve, e.g. also as a microphase-separated system via a stable over a very long period of time and the adhesion does not deteriorate. This is especially true for longer Storage at elevated Temperatures.

Farther the requirements of the end customers continue to rise. So is e.g. the flatness of the electrical module with the card body important criterion, otherwise the cards are no longer read could become. This implies that the implantation temperatures are limited to the top are, since e.g. especially PVC at implant temperatures above 170 ° C too Deformations tends.

This is a special problem for on nitrile rubber-based adhesives, since these themselves in conjunction require very high activation temperatures with phenolic resins and only a low flow behavior exhibit.

One Another criterion is the requirement from the banking sector that The electrical modules can not be removed non-destructively. Accordingly, the internal cohesion of the adhesive must be very high, so he does not split in the middle and liability to both Pages (card body + electrical module) is extremely high. At the same time, the glue needs also a very high flexibility show, as the cards after implanting torsion tests and Go through bending test. The map material should be preferred first break before the adhesion to the card body and the electric module exposes. As a rule, not even withdrawals are made at the edge tolerated.

One Another criterion is temperature fluctuations and the influence of moisture, as these cards in the later Use both high and low temperatures to withstand and sometimes even have to survive a wash passage. Accordingly, should the adhesive does not embrittle at low temperatures, at high temperatures do not liquefy and have a low tendency to absorb water.

One Another requirement criterion is due to the growing number of Card requirements the processing speed. The glue should very quickly soften or melt, thus the implantation process can be completed within one second.

In view of this state of the art, the invention is based on the object of specifying an adhesive film for implanting electrical modules in a card body, which mentioned above met criteria and in particular at implant temperatures of 150 ° C in the stamp to the different card bodies and electrical modules forms a very high adhesion.

• a) der Blend mikrophasensepariert ist
• b) der Blend zumindestens 2 Erweichungstemperaturen besitzt, wobei zumindestens eine Erweichungstemperatur größer 65°C und kleiner 125°C ist
• c) einen nach Testmethode A gemessenen G' bei 23°C von größer 10⁷ Pas besitzt
• d) einem nach Testmethode A gemessenen G'' bei 23°C von größer 10⁶ Pas besitzt
• e) und einen nach Testmethode A gemessenen crossover von kleiner 125°C aufweist.

According to the invention the object is achieved by an adhesive film consisting of a blend of a synthetic rubber S1 and a thermoplastic 2, wherein

• a) the blend is microphase-separated
• b) the blend has at least 2 softening temperatures, wherein at least one softening temperature is greater than 65 ° C and less than 125 ° C
• c) has a measured by test method A G 'at 23 ° C greater than 10 ⁷ Pas
• d) has a measured by test method A G '' at 23 ° C greater than 10 ⁶ Pas
• e) and a measured by test method A crossover of less than 125 ° C.

Farther the crossover temperature must be below 125 ° C, otherwise the adhesive do not become fluid and therefore not the map surface and wet the electrical module optimally.

Furthermore, the elastic component G 'must be greater than 10 ⁷ Pas and the viscous component G "must be greater than 10 ⁶ Pas, since otherwise optimal flexibility of the adhesive is not guaranteed Therefore, a rheologically optimized viscoelastic behavior is required.

By the mixture according to the invention the blend achieves an improvement in the adhesion to the card body, which is optimal to achieve with a blend.

• f) der Blend mikrophasensepariert ist
• g) der Blend zumindestens 2 Erweichungstemperaturen besitzt, wobei zumindestens eine Erweichungstemperatur größer 65°C und kleiner 125°C ist
• h) einen nach Testmethode A gemessenen G' bei 23°G von größer 10⁷ Pas besitzt
• i) einen nach Testmethode A gemessenen G'' bei 23°C von größer 10⁶ Pas besitzt
• j) und einen nach Testmethode A gemessenen crossover von kleiner 125°C aufweist.

In a further preferred embodiment of the invention, an adhesive film is used for implanting electrical modules with card bodies, the adhesive film consisting of a blend of a nitrile rubber and a thermoplastic T2, and

• f) the blend is microphase-separated
• g) the blend has at least 2 softening temperatures, wherein at least one softening temperature is greater than 65 ° C and less than 125 ° C
• h) has a measured by test method A G 'at 23 ° G greater than 10 ⁷ Pas
• i) has a measured by test method A G '' at 23 ° C greater than 10 ⁶ Pas
• j) and has a measured by test method A crossover of less than 125 ° C.

• a) der Nitrilkautschuk eine Erweichungs/Glasübergangstemperatur von –80 bis 0°C besitzt
• b) der Thermoplast eine Erweichungs-/Glasübergangstemperatur von 65°C bis 125 °C besitzt
• c) der Nitrilkautschuk in dem Thermoplasten unlöslich ist.

In a further very preferred embodiment of the invention, microphase-separated blends of nitrile rubber and thermoplastic are used, wherein

• a) the nitrile rubber has a softening / glass transition temperature of -80 to 0 ° C
• b) the thermoplastic has a softening / glass transition temperature of 65 ° C to 125 ° C
• c) the nitrile rubber is insoluble in the thermoplastic.

Under Softening temperature is here a glass transition temperature for amorphous Systems and a melting temperature in semicrystalline polymers be understood. The temperatures given here correspond those that are quasi-stationary Experiments, e.g. DSC, to be obtained.

Of the Weight fraction of the nitrile rubber in the thermoplastic is preferred between 2 and 60% by weight, more preferably between 5 and 50 %.

The bonding of the electrical module with a card body. for producing a so-called smart card is in 1 ) shown schematically. The inventive temperature-activatable adhesive in a preferred embodiment has a layer thickness between 10 and 100 microns, in a particularly preferred embodiment, a layer thickness of 30 to 80 microns.

By the mixture with the synthetic rubber S1 will be a reduction of the viscosity achieved under implant conditions. The mass flows thus not - yourself at increase of implantation - off the cavity the card and carries thus complete for bonding.

Synthetic rubbers S1

Of the Innovative heat-activatable adhesive consists of a blend of at least one synthetic rubber S1 and at least one thermoplastic polymer T2.

In a very preferred embodiment, as synthetic rubbers S1, polyvinyl butyral, polyvinyl formal, nitrile rubbers, nitrile butadiene rubbers, hydrogenated nitrile butadiene rubbers, polyacrylate rubbers, chloroprene rubbers, ethylene-propylene-diene rubbers, methyl-vinyl silicone rubbers, fluorosilicone rubbers, tetrafluoroethylene Propylene copolymer rubbers, butyl rubbers, styrene-butadiene rubbers used. Nitrile butadiene rubbers are available on Europrene ^™ from Eni Chem, or under Krynac ^™ from Bayer, or as Breon ^™ and Nipol N ^™ from Zeon. Polyvinyl butyrals are available under Butvar ^™ from Solucia, under Pioloform ^™ from Wacker and under Mowital ^™ from Kuraray. Hydrogenated nitrile-butadiene rubbers are available under Therban ^™ from Bayer and Zetpol ^™ from Zeon. Polyacrylate rubbers are available under Nipol AR ^™ from Zeon. Chloroprene rubbers are available under Baypren ^™ from Bayer. Ethylene-propylene-diene rubbers are available under Keltan ^™ from DSM, under Vistalon ^™ from Exxon Mobile and under Buna EP ^™ from Bayer. Methyl vinyl silicone rubbers are available under Silastic ^™ from Dow Corning and Silopren ^™ . available from GE Silicones. Fluorosilicone rubbers are available under Silastic ^™ from GE Silicones. Butyl rubbers are available under Esso Butyl ^™ from Exxon Mobile. Styrene-butadiene rubbers are available under Buna S ^™ from Bayer, and Europrene ^™ from Eni Chem and under Polysar S ^™ from Bayer.

Polyvinylformals are available under Formvar ^™ from Ladd Research: Synthetic rubbers S1 in a preferred embodiment have a softening / glass transition temperature between -80 and 0 ° C.

Thermoplastics T2:

The thermoplastic materials are preferably selected from the group of the following polymers are chosen: Polyurethanes, polystyrene, acrylonitrile-butadiene-styrene terpolymers, Polyesters, hard polyvinyl chlorides, soft polyvinyl chlorides, polyoxymethylenes, Polybutylene terephthalates, polycarbonates, fluorinated polymers, such as. Polytetrafluoroethylene, polyamides, ethylene vinyl acetates, polyvinyl acetates, Polyimides, polyethers, copolyamides, copolyesters, polyolefins, such as e.g. Polyethylene, polypropylene, polybutene, polyisobutene, and poly (metha) crylate. The list is not exhaustive.

The Synthetic rubbers have a preferred design Softening / glass transition temperature between +60 and 125 ° C.

to Optimization of the adhesive properties and the activation range Optionally, adhesive-enhancing resins or reactive resins can be used added sat. The proportion of resins is between 2 and 50 wt .-% based on the blend.

When all tackifying resins to be added are all previously known and adhesive resins described in the literature can be used. Called are representative of the pinene, indene and rosin resins whose disproportionated, hydrogenated, polymerized, esterified derivatives and salts, the aliphatic and aromatic hydrocarbon resins, Terpene resins and terpene phenolic resins and C5, C9 and other hydrocarbon resins. Any combination of these and other resins may be used to adjust the properties of the resulting adhesive as desired. In general, all with the appropriate thermoplastics T2 us rubbers S1 compatible (soluble) resins, in particular Reference is made to all aliphatic, aromatic, alkylaromatic Hydrocarbon resins, hydrocarbon resins based on pure Monomers, hydrogenated hydrocarbon resins, functional hydrocarbon resins as well as natural resins. On the representation of the knowledge in the "Handbook of Pressure Sensitive Adhesive Technology "by Donatas Satas (van Nostrand, 1989) be explicit pointed.

In another embodiment Reactive resins are added to the blend. A very preferred group includes epoxy resins. The molecular weight of the epoxy resins varies from 100 g / mol up to a maximum of 10,000 g / mol for polymeric epoxy resins.

The Epoxy resins include, for example, the reaction product of bisphenol A and epichlorohydrin, the reaction product of phenol and formaldehyde (Novolak resins) and epichlorohydrin, glycidyl ester, the reaction product from epichlorohydrin and p-amino phenol.

Preferred commercial examples include Araldite ^™ 6010, CY-281 ^™ , ECN ^™ 1273, ECN ^™ 1280, MY 720, RD-2 from Ciba Geigy, DER ^™ 331, DER ^™ 732, DER ^™ 736, DEN ^™ 432, DEN ^™ 438, ^TM 485 from Dow Chemical, Epon ^™ 812, 825, 826, 828, 830, 834, 836, 871, 872,1001, 1004, 1031 etc. from Shell Chemical and HPT ^™ 1071, HPT ^™ 1079 also from Shell Chemical.

Examples of commercial aliphatic epoxy resins are, for example, vinylcyclohexanedioxides, such as ERL-4206, ERL-4221, ERL 4201, ERL-4289 or ERL-0400 from Union Carbide Corp.

As the novolak resins, for example, Epi-Rez ^™ 5132 from Celanese, ESCN-001 from Sumitomo Chemical, CY-281 from Ciba Geigy, DEN ^™ 431, DEN ^™ 438, Quatrex 5010 from Dow Chemical, RE 305S from Nippon Kayaku can be used , Epiclon ^™ N673 from DaiNipon Ink Chemistry or Epicote ^™ 152 from Shell Chemical.

Furthermore, can be used as reactive resins and melamine resins, such as Cymel ^TM 327 and 323 from Cytec.

Furthermore, can be used as reactive resins and terpene phenolic resins such as NIREZ ^TM 2019 from Arizona Chemical.

Farther can be used as reactive resins and phenolic resins, such. YP 50 of Toto Kasei, PKHC of Union Carbide Corp. And BKR 2620 from Showa Union Gosei Corp. deploy.

It is also possible to use as reactive resins also polyisocyanates such as Coronate ^™ L from Nippon Polyurethane Ind., Desmodur ^™ N3300 or Mondur ^™ 489 from Bayer.

Around to accelerate the reaction between the two components Also optional crosslinker and accelerator in the mix too additize.

When Accelerators are useful e.g. Imidazoles, commercially available at 2M7, 2E4MN, 2PZ-CN, 2PZ-CNS, P0505, L07N from Shikoku Chem. Corp. or Curezol 2MZ from Air Products.

Farther It is also possible to use amines, in particular tertiary amines for acceleration deploy.

Next Reactive resins can also use plasticizers. Here you can in a preferred embodiment plasticizers based on polyglycol ethers, polyethylene oxides, Phosphate esters, aliphatic carboxylic acid esters and benzoic acid esters be used. Furthermore, it is also possible to use aromatic carboxylic esters, high molecular weight Diols, sulfonamides and adipic acid esters deploy.

Farther can optional fillers (e.g., fibers, carbon black, Zinc oxide, titanium dioxide, chalk, solid or hollow glass spheres, microspheres other materials, silica, Silicates), nucleating agents, blowing agents, Compounding agents and / or anti-aging agents, e.g. in shape from primary and secondary Antioxidants or be added in the form of sunscreens.

In a further preferred embodiment, polyolefins, in particular poly-α-olefins, are added to the blend. Different heat-activatable poly-α-olefins are commercially available from Degussa under the trade name Vestoplast ^™ .

In a preferred embodiment, the blends have static softening temperatures T _{E, A} or melting points T _{S, A} of +65 ° C to 125 ° C. The adhesive power of these polymers can be increased by targeted additive. For example, polyimine or polyvinyl acetate copolymers can be used as adhesives-promoting additives.

method for the production

The inventive blends can out of solution or produced in the melt. For the production of the blend in solution are preferred solvents used, in which at least one of the components a good solubility having. To prepare the mixture, the known stirring units are used. Therefor can also be the entry of heat to be required. Subsequently the blends are out of solution or more preferably melt-coated. For the coating from the melt, the solvent is previously removed from the blend. In a preferred embodiment becomes the solvent withdrawn under reduced pressure in a concentrating extruder, For example, single or twin screw extruder used can be which prefers the solvent Distill off in different or equal vacuum stages and over a feed preheater feature. Then it will over a melt nozzle or an extrusion die coated, where appropriate, the adhesive film is stretched to to achieve the optimum coating thickness.

In a further embodiment of the invention, the blend is prepared in the melt. For the Vermi A resin mixer or a twin-screw extruder or a planetary roller extruder can be used.

The Coating then takes place again from the melt. It is about one melt die or an extrusion die coated, where appropriate, the adhesive film is stretched to to achieve the optimum coating thickness.

When support materials for the Blend are the familiar and common to those skilled materials, such as films (Polyester, PET, PE, PP, BOPP, PVC, polyimide), nonwovens, foams, fabrics and tissue films and release paper (glassine, HDPE, LDPE). The carrier materials should be equipped with a separating layer. The separation layer consists in a very preferred embodiment of the invention of a Silicone release varnish or a fluorinated release varnish.

Examples

Test Methods:

Rheology A)

The Measurement was carried out with a rheometer from Rheometrics Dynamic Systems (RDA II). The sample diameter was 8 mm, the sample thickness was between 1 and 2 mm. It was measured with the plate on plate configuration. It became the temperature sweep from 0-150 ° C with a Frequency of 10 rad / s recorded.

Iso-bending B)

Of the Iso-bending test is analogous to Iso / IEC standard 10373: 1993 (E) - section 6.1 performed. The test is passed when a total of more than 4000 bends be achieved.

Extreme bending test C)

in the Extreme stress test is a 3 cm wide cutout with the electric Module lying in the middle cut out of the chip card and then 10 × of 3 cm wide compressed to 2.5 cm width. The test is passed, if the electric. Module does not dissolve.

Hand test D)

in the Hand the chip card with your hand over one of the two corners, the closer lie to the electrical module, so far bent until that the card breaks or the module breaks. Then the test is passed. If the electric module comes loose or falls out, the rule applies the test failed.

Reference 1)

• Polyamide film XAF 34.408 from Collano-Xiro

Reference 2)

• PU film XAF 36.304 from the company Collano Xiro

example 1

30 % By weight of Breon N41 N80 (nitrile rubber) from Zeon and 70% by weight Platamid 2395 (Copolyamide) from Atofina were in a measuring kneader The company Haake at about 130 ° C. and 15 minutes at 25 rpm. mixed. The heat-activatable Adhesive was subsequently pressed between two layers of siliconized Glassine release paper to 60 microns at 140 ° C.

Example 2

30% by weight of Breon N41 N80 (nitrile rubber) from Zeon and 70% by weight of Grilltex 1365 (copolyester) from EMS-Griltech were added to a measuring kneader from Haake at about 130 ° C. and for 15 minutes 25 rpm. mixed. The heat-activatable adhesive was then pressed between two layers of siliconized Glassine release paper to 60 microns at 140 ° C.

Example 3

40 % By weight of Breon N41 N80 (nitrile rubber) from Zeon and 60% by weight Grilltex 1365 (copolyester) from the company EMS-Griltech were in a Recording Extruder The company Haake at about 130 ° C. and 15 minutes at 25 rpm. mixed. The heat-activatable Adhesive was subsequently pressed between two layers of siliconized Glassine release paper to 60 microns at 140 ° C.

Implantation of electrical modules

The Implantation of the electrical modules took place in the card body with a Implanter of the company Ruhlamat Testplatz Modul insert.

The following materials were used.
Electrical Modules: Nedcard Dummy N4C-25C, Tape Type: 0232-10
PVC cards: Fa. CCD
ABS card: Fa.ORGA

In a first step will be over a Zweiwalzenkaschieranlage Fa. Storck GmbH the examples 1 to 3 with 2 bar on the module belt of Fa. Nedcard laminated.

Then The electrical modules are implanted in the appropriate cavity of the card body. There were the following parameters for all examples applied:

Heating steps: 1

• Stamping temperature: 150 ° C
• Time: 1 × 2 s
• Cooling step: 1 × 800 ms, 25 ° C
• Pressure: 70 N per module

Results:

The With the inventive adhesives manufactured chip cards were tested according to the test methods B, C and D. The results are shown in Table 1.

table 1 it can be seen that all the inventive examples the most important criteria for have passed a chip card and thus very good for bonding of electric modules on card bodies are suitable.

Tab. 2

The Reference patterns in Table 2, on the other hand, are significantly worse and In particular, on ABS card materials do not pass the test methods.

Claims (11)

Adhesive film, consisting of a blend of a synthetic rubber S1 and a thermoplastic 2, wherein a) the blend is microphase-separated b) the blend has at least 2 softening temperatures, wherein at least one softening temperature greater than 65 ° C and less than 125 ° C c) one after Test method A measured G 'at 23 ° C greater than 10 ⁷ Pas has d) one measured by test method A G''at 23 ° C greater than 10 ⁶ Pas has e) and measured by test method A crossover of less than 125 ° C. , for bonding electrical modules in chip cards. Adhesive film used for implanting electrical modules with card bodies, wherein the adhesive film consists of a blend of a nitrile rubber and a thermoplastic T2, and k) the blend is microphase-separated l) the blend has at least 2 softening temperatures, wherein at least one softening temperature greater than 65 ° C and less than 125 ° C., m) has a G 'measured according to test method A at 23 ° C. of greater than 10 ⁷ Pas n) has a G''measured according to test method A at 23 ° C. of greater than 10 ⁶ Pas o) and one according to the test method A measured crossover of less than 125 ° C. Adhesive film for implantation of electrical Modules with card bodies used, wherein the adhesive film as mikrophasenseparierter Blend of nitrile rubber and thermoplastic is used, wherein d) the nitrile rubber has a softening / glass transition temperature of -80 to 0 ° C possesses e) the thermoplastic has a softening / glass transition temperature of 65 ° C to 125 ° C f) the nitrile rubber is insoluble in the thermoplastic. Adhesive film after at least one of the preceding Claims, characterized in that the layer thickness between 10 and 100 microns, especially preferably between 30 and 80 microns is. Adhesive film after at least one of the preceding Claims, characterized in that the thermoplastics T2 are particularly preferred from the groups of copolyamides, polyethylvinyl acetates, polyvinyl acetates, Polyolefins, polyurethanes and copolyesters can be selected Adhesive film after at least one of the preceding Claims, characterized in that as synthetic rubbers S1 polyvinyl butyral, Polyvinylformal, Nitrile Rubbers, Nitrile Butadiene Rubbers, Hydrogenated Nitrile-butadiene rubbers, polyacrylate rubbers, chloroprene rubbers, Ethylene-propylene-diene rubbers, methyl-vinyl-silicone rubbers, Fluorosilicone rubbers, tetrafluoroethylene-propylene copolymer rubbers, Butyl rubbers, styrene-butadiene rubbers are used. Adhesive film after at least one of the preceding Claims, characterized in that additionally as reactive resins epoxy, and / or phenolic and / or novolac resins are used. Process for making a heat-activatable Adhesive tape, characterized in that the adhesive film after the claims 1 to 7 coated on a release paper or a release film becomes. Use of the heat-activatable prepared by process 8 Adhesive tape Adhesive film for bonding to polyimide, polyester or epoxy-based chip modules and on PVC, ABS, PET, PC, PP or PE card bodies. Method according to claim 8, characterized in that that the heat-activatable adhesive tape is punched. Method according to at least one of the preceding Claims, characterized in that the heat-activatable adhesive tape with an implantation stamping temperature of 150 ° C is processed.