EP1913107A1 - Film adhesif a base de melanges de caoutchouc nitrile destine a la fixation d'elements metalliques sur des matieres plastiques - Google Patents

Film adhesif a base de melanges de caoutchouc nitrile destine a la fixation d'elements metalliques sur des matieres plastiques

Info

Publication number
EP1913107A1
EP1913107A1 EP06778009A EP06778009A EP1913107A1 EP 1913107 A1 EP1913107 A1 EP 1913107A1 EP 06778009 A EP06778009 A EP 06778009A EP 06778009 A EP06778009 A EP 06778009A EP 1913107 A1 EP1913107 A1 EP 1913107A1
Authority
EP
European Patent Office
Prior art keywords
heat
resins
nitrile rubber
rubbers
nitrile
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP06778009A
Other languages
German (de)
English (en)
Inventor
Marc Husemann
Frank Hannemann
Matthias Koop
Thilo Dollase
Thorsten Krawinkel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tesa SE
Original Assignee
Tesa SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tesa SE filed Critical Tesa SE
Publication of EP1913107A1 publication Critical patent/EP1913107A1/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C09J123/36—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2409/00—Presence of diene rubber
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2813—Heat or solvent activated or sealable

Definitions

  • the invention relates to a blend of at least three nitrile rubbers of different composition and a reactive resin for bonding metal parts to plastics in portable consumer electronics articles, which have a high bond strength and shock resistance after bonding even at low temperatures below -15 ° C.
  • double-sided pressure-sensitive adhesive tapes are usually used.
  • the adhesive forces required for this purpose are sufficient for fixing and fastening the metal components on the plastics.
  • the metals used are usually steel, stainless steel and aluminum.
  • the plastics used are, for example, PVC, ABS, PC or blends based on these plastics.
  • the demands are steadily increasing. On the one hand, these articles are getting smaller and smaller so that the bond areas are automatically reduced as well.
  • the bonding must also meet additional requirements, since portable articles are used in a wider temperature range and can also be exposed to a case. These requirements are particularly problematic for metal bonding on plastics.
  • the plastic can absorb part of the energy in a case, while metals do not deform at all.
  • Heat-activatable adhesive films require heat application for bonding (for adhesive layer formation) and usually - as with all pressure-sensitive self- or pressure-sensitive adhesives - a certain application of pressure (therefore they should not be confused with hot-curing reaction adhesives, which harden when heat is applied and therefore not are to be regarded as self-adhesive masses). Heat-activatable adhesives can be divided into two categories:
  • thermoplastic heat-activatable films b) reactive heat-activatable films
  • thermoplastic heat-activated films have been known for a long time and are based e.g. on polyesters or copolyamides. Commercial examples of these are 3M 615, 3M 615S or tesa 8440. However, these thermoplastic heat-activatable films also have disadvantages for use in portable consumer electronics articles. This applies in particular to the oozing behavior under application of pressure under temperature, because in the application always diecuts are processed, which then change their shape.
  • the nitrile rubber gives the heat-activatable film high dimensional stability and, as a result of the crosslinking reaction, enables high bond strengths on metals and plastics.
  • the high dimensional stability and the low fluidity also have disadvantages: Due to the high strength, the heat-activatable film hardens very quickly at low temperatures and becomes brittle with the result that the bond becomes shock-sensitive at very low temperatures and rises.
  • the invention is based on the object of providing a heat-activatable adhesive film for fastening metal parts to plastics for portable consumer electronics, which withstands a cold shock test at -20 ° C and a high bond strength in a temperature range of -20 0 C to +50 0 C.
  • the object is achieved by a heat-activatable adhesive film which is provided with an adhesive comprising a blend ("a mixture") of at least three synthetic nitrile rubbers S1, S2 and S3 and at least one reactive resin which is crosslinkable with itself, with others Reactive resins and / or with the nitrile rubbers S1, S2 and S3 capable, wherein a) the blend of heat-activatable film is microphase-separated, characterized by at least three different glass transition temperatures in DSC b) the blend of heat-activatable film has at least 3 glass transition temperatures, wherein at least one glass transition temperature greater than 10 0 C and a glass transition temperature of less than -20 0 C, c) the one or more nitrile rubbers S1 an acrylonitrile fraction of greater than / equal to 35% having d) the one or more nitrile rubbers S2 having an acrylonitrile fraction of greater than 25% and less than 35% e) the or the nitrile rubbers
  • phase separation in which several similar (“compatible") polymers assemble, and when the domains are of the order of the original polymers one speaks of microphase separation (also microphase separation or microphase separation).
  • the inventive composition has a drop height of greater than 1 m at RT and greater than 25 measured according to test method A. cm at -20 ° C and / or measured by test method B bond strength of greater than 2 N / mm 2 at room temperature and greater than 3 N / mm 2 at -20 ° C.
  • the inventive blend of the blend improves the adhesive properties at low and high temperatures.
  • microphase separation and the formation of 3 Glass transition temperatures at very low temperatures (less than -20 0 C) and at high temperatures (> 10 "C) supported by a broadly distributed average glass transition temperature) results in an advantageous interaction of the adhesive properties of the individual components.
  • the low glass transition temperature domain increases cold impact strength and low temperature adhesion, while the high temperature domain provides high temperature bond strength and dimensional stability of the die under pressure and temperature.
  • the glass transition temperatures reported herein correspond to those resulting from quasi-stationary experiments, such as e.g. the differential scanning calometry, DSC, can be obtained.
  • the proportion by weight of nitrile rubber (s) S1 is preferably between 5 and
  • nitrile rubber (s) S2 is preferably between 10 and
  • nitrile rubber (s) S3 is preferably between 5 and
  • heat-activatable films having a layer thickness between 25 and 300 ⁇ m, and in a particularly preferred design a layer thickness of 50 to 250 ⁇ m, are used for the bonding of the metal parts to the plastics.
  • the adhesive used for the heat-activatable adhesive film according to the invention consists of a blend of at least three nitrile rubbers S1, S2 and S3.
  • Nitrile rubbers S1 Nitrile butadiene rubbers are available as Europrene TM from Eni Chern, or as Krynac TM and Perbunan TM from Bayer, or as Breon TM and Nipol N TM from Zeon. Hydrogenated nitrile-butadiene rubbers are available under Therban TM from Bayer and Zetpol TM from Zeon. Nitrile butadiene rubbers are polymerized either hot or cold.
  • the nitrile rubbers S1 have an acrylonitrile content of greater than 35%. However, in order to avoid complete phase separation, the proportion of acrylonitrile should again be less than 60%, based on the total content of S1.
  • a further criterion is the glass transition temperature of the nitrile rubbers S1.
  • the static glass transition temperature in the DSC should be greater than or equal to -20 ° C., more preferably greater than -15 ° C.
  • Another criterion for the nitrile rubber S1 is the Mooney viscosity. Since high flexibility at low temperatures must be ensured, the Mooney viscosity should be below 120 (Mooney ML 1 + 4 at 100 ° C.) Commercial examples of such nitrile rubbers include Nipol TM 40-5 from Zeon Chemicals.
  • Nitrile butadiene rubbers are available as Europrene TM from Eni Chem, or as Krynac TM and Perbunan TM from Bayer, or as Breon TM and Nipol N TM from Zeon. Hydrogenated nitrile-butadiene rubbers are available under Therban TM from Bayer and Zetpol TM from Zeon. Nitrile butadiene rubbers are polymerized either hot or cold.
  • the nitrile rubbers S2 have an acrylonitrile content of less than 35% and more than 25%. Another criterion is the glass transition temperature of the nitrile rubbers S2.
  • the static glass transition temperature in DSC at less than -20 0 C, more preferably less than -25 ° C.
  • Another criterion for the nitrile rubber S2 is the Mooney viscosity. Since high flexibility at low temperatures must be ensured, the Mooney viscosity should be below 100 (Mooney ML 1 + 4 at 100 0 C).
  • Commercial examples of such nitrile rubbers are, for example, Breon TM N33C50 from Zeon Chemicals.
  • Nitrile butadiene rubbers are available as Europrene TM from Eni Chem, or as Krynac TM and Perbunan TM from Bayer, or as Breon TM and Nipol N TM from Zeon. Hydrogenated nitrile-butadiene rubbers are available under Therban TM from Bayer and Zetpol TM from Zeon. Nitrile butadiene rubbers are polymerized either hot or cold.
  • the Nitrile rubbers S3 have an acrylonitrile content of less than 25%. However, in order to avoid complete phase separation, the acrylonitrile content should be greater than 4%, again based on the total content of S3. Another criterion is the glass transition temperature of the nitrile rubbers S3.
  • the static glass transition temperature in DSC at less than / equal to -35 ° C, more preferably be at less than -40 0 C.
  • Another criterion for the nitrile rubber S3 is the Mooney viscosity. Since high flexibility at low temperatures must be ensured, the Mooney viscosity should be below 100 (Mooney ML 1 + 4 at 100 ° C).
  • Commercial examples of such nitrile rubbers include Nipol TM 1034-60 from Zeon Chemicals.
  • the Nitrilkautschukblend be added according to the invention reactive resins.
  • Reactive resins are to be understood as meaning those resins which have functional groups which can undergo chemical reactions, in particular by thermal activation.
  • the reactive resins used according to the invention are in particular capable of crosslinking with themselves, with other reactive resins and / or with the nitrile rubbers S1, S2 and S3.
  • non-reactive resins that can be added as additives, are essentially physically mixed with the adhesive and remain on activation and can significantly influence, for example, the viscoelastic properties.
  • the proportion of reactive resins is between 75 and 30 wt .-% based on the total mixture of Nitrilkautschukblend and reactive resin.
  • a very preferred group of reactive resins to be used includes epoxy resins.
  • the molecular weight M w of the excellently usable epoxy resins is in particular from 100 g / mol up to a maximum of 10,000 g / mol for polymeric epoxy resins.
  • Highly useful epoxy resins include, for example, epichlorohydrin, glycidyl esters, the reaction product of epichlorohydrin and p-amino phenol, and the reaction product of bisphenol A and epichlorohydrin.
  • Preferred commercial examples are e.g. Araldite TM 6010, CY-281 TM, ECN TM 1273, ECN TM 1280, MY 720, RD-2 from Ciba Geigy, DER TM 331, THE TM 732, THE TM 736, THE TM 432, THE TM 438, THE TM 485 from Dow Chemical, Epon TM 812, 825, 826, 828, 830, 834, 836, 871, 872,1001, 1004, 1031 etc. from Shell Chemical and HPT TM 1071, HPT TM 1079 also from Shell Chemical.
  • Examples of advantageous commercial aliphatic epoxy resins are e.g. Vinylcyclohexane dioxides such as ERL-4206, ERL-4221, ERL 4201, ERL-4289 or ERL-0400 from Union Carbide Corp.
  • novolak resins e.g. Epi-Rez TM 5132 from Celanese, ESCN-001 from Sumitomo Chemical, CY-281 from Ciba Geigy, DEN TM 431, DEN TM 438, Quatrex 5010 from Dow Chemical, RE 305S from Nippon Kayaku, Epiclon TM N673 from DaiNippon Ink Chemistry or Epikote TM 152 from Shell Chemical.
  • melamine resins can also be used excellently as reactive resins, such as, for example, melamine resins.
  • terpene phenolic resins such as e.g. Use NIREZ TM 2019 from Arizona Chemical.
  • reactive resins it is also possible to use phenolic resins, e.g. YP 50 from Toto Kasei, PKHC from Union Carbide Corp. and BKR 2620 from Showa Union Gosei Corp. deploy. Further advantageous can be used as reactive resins and phenolic resole resins in combination with other phenolic resins.
  • polyisocyanates such as Coronate TM L from Nippon Polyurethane Ind., Desmodur TM N3300 or Mondur TM 489 from Bayer.
  • crosslinkers and accelerators can optionally be added to the mixture in a favorable procedure.
  • Suitable accelerators are e.g. Imidazoles, commercially available as 2M7, 2E4MN, 2PZ-CN, 2PZ-CNS, P0505, L07N from Shikoku Chem. or Curezol 2MZ from Air Products.
  • Further suitable crosslinkers are HMTA (hexamethylenetetramine) additives.
  • amines in particular tert. -Amine use for acceleration.
  • tackifier resins or further reactive resins are optionally possible to add to optimize the adhesive properties and the activation range.
  • tackifying resins to be added all previously known adhesive resins described in the literature can be used without exception. Mention may be made representative of the pinene, indene and rosin resins, their 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 can be used to adjust the properties of the resulting adhesive as desired.
  • plasticizers can also be used.
  • plasticizers based on polyglycol ethers, polyethylene oxides, phosphate esters, aliphatic carboxylic acid esters and benzoic acid esters can be used.
  • aromatic carboxylic esters, relatively high molecular weight diols, sulfonamides and adipic esters can be used.
  • optional fillers eg fibers, carbon black, zinc oxide, titanium dioxide, chalk, solid or hollow glass spheres, microspheres of other materials, silica, silicates
  • nucleating agents eg fibers, carbon black, zinc oxide, titanium dioxide, chalk, solid or hollow glass spheres, microspheres of other materials, silica, silicates
  • blowing agents eg., adhesive-enhancing additives and thermoplastics
  • compounding agents and / or aging inhibitors eg Form of primary and secondary antioxidants or in the form of sunscreens.
  • further additives are added to the blend, e.g. Polyvinylformal, polyacrylate rubbers, chloroprene rubbers, ethylene-propylene-diene rubbers, methyl-vinyl-silicone rubbers, fluorosilicone rubbers, tetrafluoroethylene-propylene copolymer rubbers, butyl rubbers, styrene-butadiene rubbers.
  • Polyvinyl butyrals are available as Butvar TM from Solucia, under Pioloform TM from Wacker and under Mowital TM from Kuraray.
  • Polyacrylate Rubbers are available from Nipol AR TM from Zeon.
  • Chloroprene rubbers are available under Baypren TM from Bayer.
  • Ethylene-propylene-diene rubbers are available under Keltan TM from DSM, under Vistalon TM from Exxon Mobile and under Buna EP TM from Bayer.
  • Methyl vinyl silicone rubbers are available from Silastic TM from Dow Corning and Silopren TM from GE Silicones. Fluorosilicone rubbers are available as Silastic TM from GE Silicones.
  • Butyl rubbers are available on Esso Butyl TM from Exxon Mobile. Styrene-butadiene rubbers are available under Buna S TM from Bayer, and Europrene TM from Eni Chem, and under Polysar S TM from Bayer. Polyvinylformals are available on Formvar TM from Ladd Research.
  • thermoplastic materials from the group of the following polymers: polyurethanes, polystyrene, acrylonitrile-butadiene-styrene terpolymers, polyesters, hard polyvinyl chlorides, flexible polyvinyl chlorides, polyoxymethylenes, polybutylene terephthalates, polycarbonates , fluorinated polymers, such as.
  • polystyrene resin As polytetrafluoroethylene, polyamides, ethylene vinyl acetates, polyvinyl acetates, polyimides, polyethers, copolyamides, copolyesters, polyolefins, such as polyethylene, polypropylene, polybutene, polyisobutene, and poly (meth) acry- late.
  • the bond strength of the heat-activatable film can be increased by further targeted additization.
  • polyimine or polyvinyl acetate copolymers can also be used as adhesives-promoting additives.
  • the blends for the heat-activatable adhesive film according to the invention can be prepared from solution or in the melt.
  • the known stirring units such as e.g. Kneader used.
  • the entry of heat may be required.
  • the blends are coated from solution or from the melt. After coating from solution, the solvent is removed in a drying tunnel. For the coating from the melt, the solvent is previously removed from the blend.
  • the solvent is stripped off in a concentration extruder under reduced pressure, for which, for example, single- or twin-screw extruders can be used, which preferably distill off the solvent in different or the same vacuum stages and have a feed preheating. Then it is coated via a melt nozzle or an extrusion die, wherein optionally the adhesive film is stretched to achieve the optimum coating thickness.
  • the blend is prepared in the melt.
  • a kneader or a twin-screw extruder, or a planetary roller extruder can be used.
  • the coating then takes place from the melt. It is coated by means of a melt nozzle or an extrusion die, with the adhesive film optionally being stretched in order to achieve the optimum coating thickness.
  • Suitable support materials for the blend are the materials familiar to the person skilled in the art, such as films (polyester, PET, PE, PP, BOPP, PVC, polyimide), nonwovens, foams, woven and woven films and release paper (glassine, HDPE, LDPE).
  • the substrates should be equipped with a release layer.
  • the separating layer consists of a silicon contrast varnish or a fluorinated release varnish.
  • the heat-activatable adhesive is coated directly onto a release paper and then further used as transfer tape. To produce larger layer thicknesses, it may also be advantageous to laminate several layers of adhesive together. This takes place particularly preferably with the introduction of heat and pressure.
  • the bond area is 2 cm 2 . It is a 1, 5 mm thick aluminum plate (1) with a width of 2 cm with a polycarbonate (PC) plate (2) with a width of 2 cm and a layer thickness of 3 mm using a heat-activatable invention Adhesive film (3) connected.
  • PC polycarbonate
  • a 200 ⁇ m thick heat-activatable film is laminated to the aluminum with the aid of a 95 ° C hot plate. Subsequently, the release film is peeled off.
  • the heat activation is carried out with a 180 0 C hot stamping press at a pressure of 5 bar and 5 s Verpressdauer.
  • the drop test is carried out (arrows in the figure: fall direction).
  • a 50 g heavy weight (4) is attached to the PC plate.
  • the entire composite is dropped from different heights onto a steel plate (5). It determines the height at which the bonding with the heat-activatable film can still absorb the impact and the AI / PC test specimens do not fall apart.
  • the test is also carried out at different temperatures.
  • Bond strength B (see FIGS. 2 and 3)
  • the bond strength is determined by a dynamic shear test (see Fig. 2).
  • the bond area is 2 cm 2 .
  • a 200 ⁇ m thick heat-activatable film is laminated to the aluminum with the aid of a 95 ° C hot plate. Subsequently, the release film is peeled off.
  • the heat activation is carried out with a 180 ° C hot stamping press at a pressure of 5 bar and 5 s Verpressdauer.
  • test specimens are torn apart using a 10 mm / min. Tacking machine using the slowly increasing force F.
  • the measured unit is given in N / mm 2 and is the maximum force that is measured to separate the test specimens (aluminum and polycarbonate). The measurement is carried out at different temperatures: - 20 0 C, 0% humidity 23 0 C, 50% humidity 50 0 C, 50% humidity
  • Measurements are taken immediately after compression and heat activation, with approximately 30 minutes to acclimatize to the respective temperature range.
  • the heat-activatable film is used with a layer thickness of 200 microns for bonding an aluminum decorative piece on a polycarbonate mobile phone case.
  • the bond area is approx. 4 cm 2 .
  • a hot press with 180 0 C, 5 bar and 5 sec. Hardening time is used. After 24 hours, the mobile phone tray is cooled down to - 20 ° C after bonding. The specimens are then mutually twisted (twisted) at this temperature.
  • Injection system TSP AS 3000 with 100 ⁇ l injection volume
  • Nipol N 1094-80 nitrile rubber
  • phenol novolak resin Durez 33040 mixed with 8% HMTA (Rohm and Haas) and 10% by weight of the phenolic resole resin 9610 LW Fa.
  • Bakelite were prepared as a 30% solution in methyl ethyl ketone in a kneader. The kneading time was 20 h.
  • the heat-activatable adhesive was then spread from solution onto a glassine release paper and dried at 100 ° C for 10 minutes. After drying, the layer thickness was 100 ⁇ m. Two of these sheets were then laminated together with a roll laminator at 100 0 C. Subsequently, the layer thickness was 200 microns.
  • Nipol 40-5 nitrile rubber from Zeon
  • Breon N33C50 nitrile rubber
  • Nipol 1034-60 nitrile rubber
  • Bakelite were prepared as a 30% solution in methyl ethyl ketone in a kneader. The kneading time was 20 h.
  • the heat-activatable adhesive was then spread from solution onto a glassine release paper and dried at 100 ° C for 10 minutes. After drying, the layer thickness was 100 ⁇ m. Two of these layers were then laminated together with a roll laminator at 100 ° C. Subsequently, the layer thickness was 200 microns.
  • Reference Example 1 represents a heat-activatable film based on a high acrylonitrile nitrile rubber (36%).
  • Reference Example 2 is based on a nitrile rubber with a low acrylonitrile content of 23%. All examples were used under the same curing conditions for bonding aluminum to polycarbonate (PC) - an application that frequently occurs, for example, in the manufacture of mobile phones. After bonding, the samples were subjected to a drop test. The results are shown in Table 1. The respective drop height is given in cm.
  • Table 1 shows that inventive examples 3 and 4 at -20 0 C have a significantly better cold shock sensitivity, which in turn is reflected in the possible higher drop height. At room temperature, all examples have high resistance to shock.
  • Table 2 shows that, especially at low temperatures, the bond strength is highest for Inventive Examples 3 and 4. This clarifies light, that in conjunction with the excellent cold impact resistance, the inventive
  • the reference example At room temperature and +50 0 C 1, the reference example, on the highest values, since this example is based only on a nitrile rubber with a high acrylonitrile content, and thus has the lowest flow behavior in the dynamic shear test. However, the differences are relatively small compared to the inventive examples 3 and 4 and the reference example 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne des films adhésifs activables thermoactivables pourvus d'une substance adhésive, comprenant un mélange d'au moins trois caoutchoucs nitrile synthétiques S1, S2 et S3 et au moins une résine réactive apte à une réticulation avec elle-même, avec d'autres résines réactives et/OU avec les caoutchoucs nitrile S1, S2 et S3. a) le mélange du film thermoactivable est séparé en microphases et caractérisé par au moins trois températures de transition vitreuse différentes dans le DSC; b) le mélange du film thermoactivable a au moins 3 températures de transition vitreuse, au moins une température de transition vitreuse étant supérieure à 10 °C et une température de transition vitreuse étant inférieure à -20 °C; c) le ou les caoutchoucs nitrile S1 ont une fraction d'acrylnitrile supérieure ou égale à 35 %; d) le ou les caoutchoucs nitrile S2 ont une fraction d'acrylnitrile supérieure à 25 % et inférieure à 35 % ; e) le ou les caoutchoucs nitrile S3 ont une fraction d'acrylnitrile inférieure ou égale à 25 %.
EP06778009A 2005-07-28 2006-07-27 Film adhesif a base de melanges de caoutchouc nitrile destine a la fixation d'elements metalliques sur des matieres plastiques Ceased EP1913107A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005035905A DE102005035905A1 (de) 2005-07-28 2005-07-28 Nitrilkautschuk Blends zur Fixierung von Metallteilen auf Kunststoffen
PCT/EP2006/064714 WO2007012656A1 (fr) 2005-07-28 2006-07-27 Film adhesif a base de melanges de caoutchouc nitrile destine a la fixation d'elements metalliques sur des matieres plastiques

Publications (1)

Publication Number Publication Date
EP1913107A1 true EP1913107A1 (fr) 2008-04-23

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EP06778009A Ceased EP1913107A1 (fr) 2005-07-28 2006-07-27 Film adhesif a base de melanges de caoutchouc nitrile destine a la fixation d'elements metalliques sur des matieres plastiques

Country Status (9)

Country Link
US (1) US7923510B2 (fr)
EP (1) EP1913107A1 (fr)
JP (1) JP2009503176A (fr)
KR (1) KR20080044843A (fr)
CN (1) CN101228243A (fr)
DE (2) DE102005035905A1 (fr)
MX (1) MX2008000942A (fr)
TW (1) TW200712162A (fr)
WO (1) WO2007012656A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE102005025056A1 (de) * 2005-05-30 2006-12-07 Tesa Ag Nitrilkautschuk-Blends zur Fixierung von Metallteilen auf Kunststoffen
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DE102012203249A1 (de) 2012-03-01 2013-09-05 Tesa Se Verwendung eines latentreaktiven Klebefilms zur Verklebung von eloxiertem Aluminium mit Kunststoff
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DE102013217880A1 (de) 2013-09-06 2015-03-12 Tesa Se Latentreaktive Klebeprodukte mit verbesserter Stanzbarkeit und latentreaktive Klebfolienstanzlinge
DE102015215247A1 (de) * 2015-08-11 2017-02-16 Tesa Se Haftklebstoff auf Basis von Acrylnitril-Butadien-Kautschuken
DE102017203092A1 (de) * 2017-02-24 2018-08-30 Tesa Se Wiederablösbarer Haftklebestreifen
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JP2009503176A (ja) 2009-01-29
US7923510B2 (en) 2011-04-12
CN101228243A (zh) 2008-07-23
US20080166554A1 (en) 2008-07-10
TW200712162A (en) 2007-04-01
KR20080044843A (ko) 2008-05-21
WO2007012656A1 (fr) 2007-02-01

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