DK160884B - THERMO-MELTIC ADMINISTRATIVE, MAINLY CONSISTING OF AN ANTICIPATIVE ART RESIN AND THERMOPLASTIC ELASTOMERIC BLOCK COPOLYMERS CONSISTING OF BLOCKS OF POLYSTYRIC AND POLYDIAL USE - Google Patents
THERMO-MELTIC ADMINISTRATIVE, MAINLY CONSISTING OF AN ANTICIPATIVE ART RESIN AND THERMOPLASTIC ELASTOMERIC BLOCK COPOLYMERS CONSISTING OF BLOCKS OF POLYSTYRIC AND POLYDIAL USE Download PDFInfo
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- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
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- Adhesives Or Adhesive Processes (AREA)
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- Polyamides (AREA)
Description
DK 160884 BDK 160884 B
Den foreliggende opfindelse angår et termosmelteligt klæbemiddel, der hovedsageligt består af en klæbrig-gørende kunstharpiks og mindst en elastomer termoplastisk blokcopolymer bestående af blokke af polystyren og en 5 polydien. Opfindelsen angår endvidere anvendelsen af klæbemidlet som trykfølsomt klæbemiddel.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosmelt adhesive consisting mainly of an adhesive resin and at least one elastomeric thermoplastic block copolymer consisting of blocks of polystyrene and a polydiene. The invention further relates to the use of the adhesive as pressure sensitive adhesive.
Trykfølsomme i varmen smeltelige klæbemidler og selvklæbende klæbestrimler er velkendte. Man har hidtil frem-10 stillet i varmen smeltelige klæbemidler ved at sammenblande de to hovedbestanddele deri: elastomere og klæbrige kunstharpikser. De mest anvendte elastomere er: - blokcopolymere af typen A-B-A indeholdende endestillede 15 blokke af polystyren og en central blok bestående enten af polybutadien eller af polyisopren eller af poly-(ethylen-butylen), - eller copolymere i blokke i stjerneform indeholdende 20 flere grene, hvori blokkene er baseret på polystyren og polybutadien.Pressure-sensitive heat-meltable adhesives and self-adhesive adhesive strips are well known. Heretofore, hot meltable adhesives have been prepared by mixing the two main constituents therein: elastomeric and tacky resins. The most widely used elastomers are: - block copolymers of type ABA containing terminated 15 blocks of polystyrene and a central block consisting of either polybutadiene or of polyisoprene or of poly (ethylene-butylene), - or copolymers in star-shaped blocks containing 20 multiple branches, wherein the blocks are based on polystyrene and polybutadiene.
Disse blokcopolymere kan være formuleret med klæbrige kunstharpikser og med blødgøringsmidler til opnåelse af 25 trykfølsomme klæbemidler, således som det er omtalt i US patentskrift nr. 3 239 478 (Harlan) og US patenskrift nr.These block copolymers may be formulated with sticky synthetic resins and with plasticizers to obtain 25 pressure-sensitive adhesives, as disclosed in U.S. Patent No. 3,239,478 (Harlan) and U.S. Pat.
4 097 434 (Coker) og i artiklerne af J.B. Borthwick (1976 TAPPI International Hot Melt Pressure Sensitive Adhesives Short Course, Amsterdam, 3-5 Nov. 1976) og af R. Delme 30 (Technology of Plastics and Rubber Interface, Bruxelles, september 1976).4,097,434 (Coker) and in the articles by J.B. Borthwick (1976 TAPPI International Hot Melt Pressure Sensitive Adhesives Short Course, Amsterdam, 3-5 Nov. 1976) and by R. Delme 30 (Technology of Plastics and Rubber Interface, Brussels, September 1976).
Disse klæbemidler udviser gode sammenlimningsegenskaber, med en permanent sammenlimningsevne og med modstands-35 dygtighed mod afrivning, men deres modstandsdygtighed mod udflydning og mod overrivning nedsættes hurtigt ved forhøjet temperatur.These adhesives exhibit good bonding properties, with a permanent bonding ability and with tear resistance, but their resistance to flow and tear are rapidly reduced at elevated temperature.
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Det er imidlertid velkendt, at man kan forøge temperatur-bestandigheden af sammenlimninger gennemført med sådanne i varmen smeltelige klæbemidler ved tilsætning af en vis mængde krystallinske polymere med høj molekylvægt og med 5 højt smeltepunkt. Men denne tilsætning fremkalder en for voldsom forøgelse af viskositeten i smeltet tilstand og tab af evnen til permanent sammenlimning.However, it is well known that one can increase the temperature resistance of adhesives carried out with such hot melt adhesives by the addition of a certain amount of high molecular weight crystalline polymers with high melting point. However, this addition causes an excessive increase in viscosity in the molten state and loss of the ability to permanently bond.
I europæisk patentansøgning nr. EP 88932 omtales tilsæt-10 ningen af et polyamid, som er resultatet af amidificering af en diamin og dicarboxylsyre, til kombination af en klæbrig kunstharpiks og en ikke-elastomerisk blokpolymer.In European Patent Application No. EP 88932, the addition of a polyamide resulting from the amidification of a diamine and dicarboxylic acid is mentioned for the combination of a sticky synthetic resin and a non-elastomeric block polymer.
Den foreliggende opfindelse er baseret på den erfaring, 15 at klæbeegenskaberne for termosmeltelige klæbemidler af den ovenfor angivne art i betydelig grad kan forbedres ved tilsætning af polyetheramid. Klæbemidlet ifølge opfindelsen er således ejendommeligt ved det i den kendetegnende del af krav 1 anførte.The present invention is based on the experience that the adhesive properties of thermally fusible adhesives of the above type can be significantly improved by the addition of polyetheramide. Thus, the adhesive according to the invention is peculiar to that of the characterizing part of claim 1.
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Det har således vist sig, at modstandsdygtigheden ved høj temperatur af de med klæbemidlerne gennemførte sammenlimninger takket være den nævnte tilsætning i stor 25 udstrækning forbedres, uden at der forekommer et tab af den permanente sammenlimningsevne; derudover foreligger der kun en meget beskeden forhøjelse af viskositeten i smeltet tilstand.Thus, it has been found that, thanks to said addition, the high temperature resistance of the adhesives made with the adhesives is greatly improved without loss of the permanent adhesive ability; moreover, there is only a very modest increase in viscosity in the molten state.
30 De således opnåede klæbemidler kan derfor anvendes mere tilfredsstillende ved fremstillingen af klæbestrimler til de mest forskelligartede anvendelsesområder.The adhesives thus obtained can therefore be used more satisfactorily in the manufacture of adhesive strips for the most diverse applications.
Ved polyetheramid forstår man såvel statistiske poly-35 etheramider (dvs. dannet ved tilfældig sammenkædning af forskellige monomer-bestanddele) som blokpolyetheramider, dvs. dannet i blokke eller sekvenser udvisende en visBy polyetheramide is understood both statistical polyetheramides (i.e., formed by random linking of various monomeric constituents) as well as block polyetheramides, i.e. formed in blocks or sequences exhibiting a certain
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3 kædelængde af de forskellige bestanddele.3 chain length of the various components.
Blok- eller sekvenspolyetheramider, som er opnået ved blokcopolykondensation af polyamider med reaktionsdygtige 5 ender og blokpolyethere med reaktionsdygtige ender, såsom blandt andre: 1) Blokke af polyamid med diaminkædeender og blokke af polyoxyalkylener med dicarboxylsyrekædeender.Block or sequence polyetheramides obtained by block copolymer condensation of 5-end reactive polyamides and reactive-end polyethers such as, among others: 1) Polyamide blocks with diamine chain ends and blocks of polyoxyalkylenes with dicarboxylic acid chain ends.
10 2) Blokke af polyamider med dicarboxylsyrekædeender og blokke af polyoxyalkylener med diaminkædeender opnået ved cyanoethylering og hydrogenering af polyetherdioler.2) Blocks of polyamides with dicarboxylic acid chain ends and blocks of polyoxyalkylenes with diamine chain ends obtained by cyanoethylation and hydrogenation of polyether diols.
15 3) Blokke af polyamider med dicarboxylsyrekædeender og sekvenser af a,ω-dihydroxylerede alifatiske polyoxyalkylener eller polyetherdioler, idet de således opnåede poly-etheramider i dette særlige tilfælde er polyetherester-amider.3) Blocks of polyamides with dicarboxylic acid chain ends and sequences of α, ω-dihydroxylated aliphatic polyoxyalkylenes or polyether diols, the polyether etheramides thus obtained being polyetherester amides in this particular case.
2020
Sammensætningen og fremstillingen af sådanne polyether-esteramider er beskrevet i de franske patentansøgninger nr. 7 418 913 og 7 726 678 tilhørende opfinderen, og hvis indhold herved kombineres med indholdet i den foreliggen-25 de beskrivelse.The composition and preparation of such polyether ester amides are described in French Patent Applications Nos. 7,418,913 and 7,726,678 to the inventor, the contents of which are combined with the contents of the present disclosure.
De hidtil ukendte klæbemidler, som er genstand for den foreliggende opfindelse, består af mindst en blokcopoly-mer af polystyren og polydien, af klæbrige kunstharpikser 30 og af mindst et polyetheramid, hvilket polyetheramid foreligger i sådanne mængdeandele, at der er 0,1 til 50 vægtdele deraf, fortrinsvis 3 til 20 vægtdele, pr. 100 vægtdele copolymer.The novel adhesives which are the subject of the present invention consist of at least one block copolymer of polystyrene and polydiene, of sticky synthetic resins 30 and of at least one polyether amide which is present in such proportions as 0.1 to 50 parts by weight thereof, preferably 3 to 20 parts by weight, per unit weight. 100 parts by weight of copolymer.
35 Udover disse hovedbestanddele kan klæbemidlerne indeholde blødgøringsmidler, stabilisatorer over for varme eller over for lys, fyldstoffer, farvestoffer etc.35 In addition to these main constituents, the adhesives may contain plasticizers, heat stabilizers or light, fillers, dyes, etc.
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Ved en udførelsesform for opfindelsen er den blokcopoly-mere en tre-blok lineær polymer af typen A-B-A, hvori de endestillede blokke består af polystyren og den centrale blok er enten en polybutadien, eller en polyisopren eller 5 en poly(ethylen-butylen). Sådanne produkter forhandles af firmaet Shell Chemicals under navnene "CARIFLEX TR " eller "KRATON®".In one embodiment of the invention, the block copolymer is a three-block linear polymer of type A-B-A, wherein the terminal blocks consist of polystyrene and the central block is either a polybutadiene, or a polyisoprene or a poly (ethylene-butylene). Such products are sold by Shell Chemicals under the names "CARIFLEX TR" or "KRATON®".
Den copolymere kan også være sammensat af blokke af 10 polystyren og af polybutadien anbragt i stjerneform.The copolymer may also be composed of blocks of polystyrene and of polybutadiene placed in star form.
Man kan ved en anden udførelsesform blande indbyrdes blokcopolymerne, f.eks. en tre-blok styren-butadien-styren med en tre-blok styren-isopren-styren.In another embodiment, the block copolymers may be mixed, e.g. a three-block styrene-butadiene-styrene with a three-block styrene-isoprene-styrene.
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Ved en udførelsesform for opfindelsen er det til blokelastomeren knyttede polyetheramid et blokpolyetherester-amid med en molekylvægt større end 10 000, som er dannet af produktet af copolykondensationen af et α,ω-di-20 carboxylsyrepolyamid eller copolyamid udvisende en molekylvægt på 300-15000, som er anvendt i en mængde på 95-15 vægt-%, og en polyetherdiol udvisende en molekylvægt på 100-6000, fortrinsvis 200-3000, som er anvendt i en mængde på 5-85 vægt-%, hvilket produkt udviser et smel-25 tepunkt på mellem 80 og 210 °C, fortrinsvis 120-180 °C, og en viskositet i smeltet tilstand på 500-5000 Pa x sek. ved 210 °C for en forskydningshastighed på 10 s-^.In one embodiment of the invention, the polyetheramide linked to the block elastomer is a block polyetherester amide having a molecular weight greater than 10,000 formed by the product of the copolymer condensation of an α, ω-dicarboxylic acid polyamide or copolyamide having a molecular weight of 300-15000. which is used in an amount of 95-15% by weight, and a polyetherdiol having a molecular weight of 100-6000, preferably 200-3000, used in an amount of 5-85% by weight, which product has a 25 to about 80 to 210 ° C, preferably 120 to 180 ° C, and a molten state viscosity of 500-5000 Pa x sec. at 210 ° C for a shear rate of 10 s - ^.
Ved en anden udførelsesform består dette polyetherester-30 amid ved 80-20% af det omtalte polyamid eller copolyamid og 20-80% af den omtalte polyetherdiol, idet polyamidet er et polyamid 6 (PA6), som er resultatet af polykonden-sationen af caprolactam, eller et polyamid 11 (PA11) baseret på 11-aminoundecansyre, eller et PA12 baseret på 35 lauryllactam, og idet polyetherdiolen er polyoxytetra-methylenglycol (PTMG).In another embodiment, this polyetherester amide comprises 80-20% of the polyamide or copolyamide mentioned and 20-80% of the polyether diol mentioned, the polyamide being a polyamide 6 (PA6) resulting from the polycondensation of caprolactam. , or a polyamide 11 (PA11) based on 11-aminoundecanoic acid, or a PA12 based on lauryl lactam and the polyether diol being polyoxytetramethylene glycol (PTMG).
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Man kan ligeledes blande indbyrdes polyetheramiderne eller polyetheresteramiderne og således, idet man kan variere på deres sammensætning og som følge deraf deres egenskaber (blandt andet deres smeltepunkt), føre til en 5 reguleret formulering for klæbemidlet, som gør det muligt at svare til visse tekniske fordringer.It is also possible to mix the polyether amides or the polyether ester amides with one another and thus, depending on their composition and consequently their properties (including their melting point), will result in a controlled formulation for the adhesive, which will meet certain technical requirements. .
Man kan i klæbemidlerne ifølge opfindelsen anvende enhver klæbrig kunstharpiks, idet man ved, at klæbrige kunst-10 harpikser ifølge deres sammensætning og kemiske struktur fortrinsvis knytter sig til polystyrenfasen eller til elastomerfasen, hvilket er omtalt i den tekniske dokumentation udsendt af firmaet Shell Chemicals. På samme måde vil blødgøringsmidlerne, afhængigt af om det drejer sig 15 om en aromatisk eller alifatisk olie, knytte sig fortrinsvis til den ene eller den anden af blokelastomer-faserne og således modificere disses mekaniske og klæbende egenskaber.Any adhesive resin can be used in the adhesives according to the invention, knowing that sticky synthetic resins according to their composition and chemical structure are preferably associated with the polystyrene phase or the elastomer phase, as discussed in the technical documentation issued by Shell Chemicals. Similarly, depending on whether it is an aromatic or aliphatic oil, the plasticizers will preferably attach to one or the other of the block elastomer phases, thus modifying their mechanical and adhesive properties.
20 Fordelene ved den foreliggende opfindelse vil fremgå af det følgende og de eksempler, der er anført til belysning af opfindelsen.The advantages of the present invention will become apparent from the following and the examples given by way of illustration of the invention.
I den foreliggende beskrivelse og i de tilhørende patent-25 krav gælder følgende forhold: - Andelene er udtrykt i vægtdele.In the present specification and in the appended claims, the following conditions apply: - The proportions are expressed in parts by weight.
- Viskositeten i smeltet tilstand er bestemt ved hjælp af 30 et apparat Rheomat 30, som er et rotationsviskosimeter fremstillet af det svejtsiske firma Contraves.- The viscosity in the molten state is determined by means of an apparatus Rheomat 30, which is a rotational viscometer manufactured by the Swiss company Contraves.
- Blødgøringspunktet er bestemt efter kugle- og ringmetoden, således som den er defineret i den amerikanske stan- 35 dard ASTM E-28.- The softening point is determined by the ball and ring method as defined in US Standard ASTM E-28.
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- Modstandsdygtigheden mod flydning og mod forskydning måles, idet man er blevet inspireret af de respektive normer AFERA 4012 P2 og PSTG-7, ved at klæbemidlet er blevet påført et underlag (f.eks. en polyesterfolie), og 5 den således fremstillede klæbestrimmel anbringes på glas på en overflade, der måler 25 x 25 mm, ved hjælp af en 2 kg valse PSTC. Prøven anbringes i en ovn, og man ophænger i strimlen en belastning på 500 g.- The resistance to flow and shear is measured, having been inspired by the respective standards AFERA 4012 P2 and PSTG-7, by applying the adhesive to a substrate (eg a polyester foil) and applying the adhesive strip thus produced on glass on a surface measuring 25 x 25 mm, using a 2 kg roller PSTC. The sample is placed in an oven and a load of 500 g is suspended in the strip.
10 Målingen kan gennemføres på to måder: - Ovnens temperatur forøges med 5 °C/min., og man opnote-rer den temperatur, ved hvilken klæbestrimlen falder (hvilket i det følgende er betegnet ved udtrykket "tempe- 15 raturen for modstandsdygtighed mod flydning").The measurement can be carried out in two ways: - The temperature of the furnace is increased by 5 ° C / min, and the temperature at which the adhesive strip falls is recorded (which is hereafter referred to as the term "temperature resistance to flow"). ").
- Temperaturen holdes konstant (40-50-60-70 °C), og man opnoterer den tid, efter hvilket forløb klæbestrimlen falder (som i det følgende er beskrevet med udtrykket 20 "modstandsdygtighed mod flydning under isotherme forhold" ).- The temperature is kept constant (40-50-60-70 ° C) and the time after which the adhesive strip decreases is recorded (which is described below with the term 20 "resistance to flow under isothermal conditions").
- Modstandsdygtigheden mod afrivning ved 180 °C bestemmes efter normerne AFERA 4001 P 11 og PSTC-1.- The resistance to tear at 180 ° C is determined according to the standards AFERA 4001 P 11 and PSTC-1.
25 EKSEMPLERNE 1-4 I efterfølgende tabel I er anført resultaterne af de målinger, som er blevet gennemført på forskellige klæbe-30 midler med et varierende indhold af polyetheramid. Disse klæbemidler er fremstillet ved sammenblanding ved en temperatur i størrelsesordenen 150-200 °C af de forskellige bestanddele, som de består af, idet denne blanding er blevet gennemført i et ælteapparat igennem den tid, som 35 er nødvendig til opnåelse af et homogent produkt.EXAMPLES 1-4 In the following Table I, the results of the measurements taken on various adhesives having a different polyether amide content are listed. These adhesives are made by mixing at a temperature in the order of 150-200 ° C of the various constituents of which they are made, this mixture having been carried out in a kneading apparatus for the time necessary to obtain a homogeneous product.
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Disse bestanddele er: - En blokelastomer - "CARIFLEX TR 1107®", en tre-blok styren-isopren-styren-elastomer fra firmaet Shell 5 Chemicals.These components are: - A block elastomer - "CARIFLEX TR 1107®", a three-block styrene-isoprene-styrene elastomer from Shell 5 Chemicals.
tfb - En klæbriggørende kunstharpiks - "FORAL 85 ", colo-phoniumester med stærkt hydrogeneret glycerin fra firmaet Hercules.tfb - A sticky synthetic resin - "FORAL 85", colo-phonium ester with highly hydrogenated glycerine from Hercules.
10 ® - Et antioxidant "IRGANOX 1010 ", pentaerythrityl-tetra-kin (3-(3,5-di-ter-butyl-4-hydroxyphenyl)-propionat) fra firmaet Ciba Geigy.10 ® - An antioxidant "IRGANOX 1010", pentaerythrityl tetraquin (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) from the company Ciba Geigy.
15 - Et polyesteramid, som i det foreliggende tilfælde er et polyetheresteramid, der af bekvemmelighedsgrunde vil blive betegnet som PEEA-A, og som er opnået ved copoly-kondensation i overensstemmelse med den fremgangsmåde, der er beskrevet i fransk patentansøgning nr. 7 418 913, 20 ud fra 30 vægtdele af en præpolymer af PA 12-dicarboxyl-syre (opnået ud fra lauryllactam og adipinsyre) med molekylvægt 850 og 70 vægtdele polyoxytetramethylenglycol (PTMG) med molekylvægt 2000, hvilket polyetheresteramid har et logaritmisk viskositetstal på 1,80 dl/g (måling 25 gennemført ved 25 °C på en opløsning indeholdende 0,5 vægtdele af denne polymer i 10 dele m-cresol).15 - A polyesteramide, which in the present case is a polyetheresteramide which, for convenience, will be designated as PEEA-A and obtained by copolymer condensation in accordance with the process described in French Patent Application No. 7,418,913 , 20 out of 30 parts by weight of a prepolymer of PA 12-dicarboxylic acid (obtained from lauryllactam and adipic acid) of molecular weight 850 and 70 parts by weight of polyoxytetramethylene glycol (PTMG) of molecular weight 2000, which has a logarithmic viscosity number of 1.80 dl / g (measurement 25 taken at 25 ° C on a solution containing 0.5 parts by weight of this polymer in 10 parts of m-cresol).
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TABEL ITABLE I
Eksempler 12 3 4 5 --_____-Examples 12 3 4 5 --_____-
Sammensætning - vægtdele CARIFLEX TR 1107 100 100 100 100 FORAL 85 100 100 100 100 10 IRGANOX 1010 5 5 5 5 PEEA-A 0 10 20 30Composition - parts by weight CARIFLEX TR 1107 100 100 100 100 FORAL 85 100 100 100 100 10 IRGANOX 1010 5 5 5 5 PEEA-A 0 10 20 30
Fysiske egenskaberPhysical properties
15 Viskositet ved 200 °CViscosity at 200 ° C
21,5 s"1 (Pa x s) 25 35 45 3521.5 s "1 (Pa x s) 25 35 45 35
Blødgøringspunkt (°C) 92 105 110 115 20Softening point (° C) 92 105 110 115 20
Temp. for modstand mod flydning (°C) 105 110 115 120Temp. for resistance to flow (° C) 105 110 115 120
Modstand ved 40 °C 1020 3945 >4000 >4000 25 mod flydning ved 50 °C 180 430 1950 2000 isotermt ved 60 0C 13 24 140 420 (min.) ved 70 °C 5 7,5 30 50 30 -- 35 Når det drejer sig om disse fire klæbemidler, gør deres permanente klæbeevne det muligt at anvende dem industri elt som trykfølsomme klæbemidler.Resistance at 40 ° C 1020 3945> 4000> 4000 25 against flow at 50 ° C 180 430 1950 2000 isothermal at 60 ° C 13 24 140 420 (min) at 70 ° C 5 7.5 30 50 30 - 35 When When these four adhesives are used, their permanent adhesiveness makes it possible to use them in industry or pressure sensitive adhesives.
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EKSEMPLERNE 5 OG 6 I efterfølgende tabel II er anført måleresultaterne gennemført på forskellige klæbemidler fremstillet analogt 5 med eksemplerne 1-4.EXAMPLES 5 AND 6 In the following Table II, the measurement results are recorded on various adhesives prepared analogously to Examples 1-4.
Bestanddelene heri er: - en sekvens-elastomer: "CARIFLEX TR 1107 ", som allerede 10 er beskrevet, - en klæbrig kunstharpiks: "ESCOREZ 1310 ", en alifatisk petroleumsharpiks fra firmaet Esso Chimie, 15 - et blødgøringsmiddel: "SHELLFLEX 451 ", en alifatisk olie fra firmaet Shell Chemicals, © - en antioxydant: "IRGANQX 1010 ", som allerede er be skrevet, 20 - et polyetheresteramid: PEEA-A, som allerede er beskrevet .The ingredients herein are: - a sequence elastomer: "CARIFLEX TR 1107" already described 10, - a sticky synthetic resin: "ESCOREZ 1310", an aliphatic petroleum resin from Esso Chimie, 15 - a plasticizer: "SHELLFLEX 451", an aliphatic oil from Shell Chemicals, © - an antioxidant: "IRGANQX 1010" already described, 20 - a polyetheresteramide: PEEA-A, already described.
EKSEMPEL 7 25EXAMPLE 7 25
Den senere følgende tabel III angår klæbemidler, som er identiske med midlerne i eksemplerne 1-4, med den forskel, at polyetheresteramidet PEEA-A er blevet erstattet med et andet polyetheresteramid, som her vil betegnes 30 PEEA-B, og som er opnået ved copolykondensation i overensstemmelse med den fremgangsmåde, der er beskrevet i fransk patentansøgning nr. 7 418 913, ud fra 67 vægtdele af en præpolymer af PA 12-dicarboxylsyre (opnået ud fra lauryllactam og adipinsyre) med molekylvægt 2000, 35 og 23 vægtdele PTMG med molekylvægt 1000, hvilket polyetheresteramid har et logaritmisk viskositetstal på 1,60 dl/g.The following Table III relates to adhesives which are identical to the agents of Examples 1-4, with the exception that the polyetheresteramide PEEA-A has been replaced by another polyetheresteramide, herein designated 30 PEEA-B, obtained by copolymer condensation according to the method described in French Patent Application No. 7,418,913, from 67 parts by weight of a prepolymer of PA 12-dicarboxylic acid (obtained from lauryllactam and adipic acid) of molecular weight 2000, 35 and 23 parts by weight PTMG of molecular weight 1000, which polyetheresteramide has a logarithmic viscosity number of 1.60 dl / g.
TABEL IITABLE II
1010
DK 160884BDK 160884B
Eksempler 5 6 5--Examples 5 6 5--
Sammensætning - vægtdele CARIFLEX TR 1107 100 100 ESCOREX 1310 125 125 10 SHELLFLEX 451 15 15 IRGANOX 1010 5 5 PEEA-A 0 20Composition - parts by weight CARIFLEX TR 1107 100 100 ESCOREX 1310 125 125 10 SHELLFLEX 451 15 15 IRGANOX 1010 5 5 PEEA-A 0 20
Fysiske egenskaber 15 --!-Physical Properties 15 -! -
Viskositet ved 200 °CViscosity at 200 ° C
1,0 s"1 (Pa x s) 15 201.0 s "1 (Pa x s) 20
Blødgøringspunkt (°C) 115 125 20Softening point (° C) 115 125 20
Modstand mod afrivning ved 180°C (i N/cm) 0,4 0,3Resistance to tearing at 180 ° C (in N / cm) 0.4 0.3
Temp, for modstand mod 25 flydning (°C) 120 135Temp, for resistance to 25 flow (° C) 120 135
Modstand mod flydning isotermt ved 70 °C 120 250 (i minutter) 30 I tilfældet angående disse to klæbemidlér, gør den perma nente klæbende evne det muligt at anvende disse inden for 35 industrien som trykfølsomme klæbemidler.Resistance to flow isothermally at 70 ° C 120 250 (in minutes) 30 In the case of these two adhesives, the permanent adhesive capability makes it possible to use these within the industry as pressure sensitive adhesives.
TABEL IIITABLE III
χι DK 160884 BDKι DK 160884 B
Eksempler 1 7 5 -----—Examples 1 7 5 -----—
Sammensætning - vægtdele CARIFLEX TR 1107 100 100 FORAL 85 100 100 10 IRGANOX 1010 5 5 PEEA-B 0 5Composition - parts by weight CARIFLEX TR 1107 100 100 FORAL 85 100 100 10 IRGANOX 1010 5 5 PEEA-B 0 5
Fysiske egenskaberPhysical properties
15 Viskositet ved 200 °CViscosity at 200 ° C
^Os^iiPaxs) 33 31^ Os ^ iiPaxs) 33 31
Blødgøringspunkt (°C) 92 98 20 Modstand ved afrivning ved 180 °C (i N/cm) 1,8 2,4Softening point (° C) 92 98 20 Tear resistance at 180 ° C (in N / cm) 1.8 2.4
Temp, for modstand mod flydning (°C) 105 110 25Temp, for resistance to flow (° C) 105 110 25
Modstand mod flydning isotermt ved 70 °CResistance to flow isotherm at 70 ° C
(i minutter) 5 15 30 -- 35 I tilfælde af disse to klæbemidler gør den permanente klæbeevne det muligt at anvende disse industrielt som trykfølsomme klæbemidler.(in minutes) 5 15 30 - 35 In the case of these two adhesives, the permanent adhesive makes it possible to use these industrially as pressure sensitive adhesives.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8415845 | 1984-10-16 | ||
| FR8415845A FR2571733B1 (en) | 1984-10-16 | 1984-10-16 | ADHESIVE COMPOSITIONS BASED ON THERMOPLASTIC ELASTOMERS AND POLYETHERAMIDES AND USES THEREOF |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| DK470585D0 DK470585D0 (en) | 1985-10-15 |
| DK470585A DK470585A (en) | 1986-04-17 |
| DK160884B true DK160884B (en) | 1991-04-29 |
| DK160884C DK160884C (en) | 1991-10-21 |
Family
ID=9308699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK470585A DK160884C (en) | 1984-10-16 | 1985-10-15 | THERMO-MELTIC ADMINISTRATIVE, MAINLY CONSISTING OF AN ANTICIPATIVE ART RESIN AND THERMOPLASTIC ELASTOMERIC BLOCK COPOLYMERS CONSISTING OF BLOCKS OF POLYSTYRIC AND POLYDIAL USE |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0179700B1 (en) |
| JP (1) | JPS61108676A (en) |
| DE (1) | DE3567223D1 (en) |
| DK (1) | DK160884C (en) |
| FI (1) | FI80902C (en) |
| FR (1) | FR2571733B1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2591607B1 (en) * | 1985-12-16 | 1988-03-18 | Atochem | THERMOPLASTIC COMPOSITIONS BASED ON POLYETHERAMIDES AND STYRENE-DIENE COPOLYMERS AND THEIR MANUFACTURING METHOD. |
| US4948825A (en) * | 1987-06-03 | 1990-08-14 | Avery International Corporation | Curable film forming compositions |
| JP2006131810A (en) * | 2004-11-08 | 2006-05-25 | Techno Polymer Co Ltd | Adhesive and adhesive film |
| KR101741292B1 (en) * | 2010-07-23 | 2017-05-29 | 다츠다 덴센 가부시키가이샤 | Adhesive agent composition and adhesive film |
| JP5675975B2 (en) * | 2011-05-31 | 2015-02-25 | タツタ電線株式会社 | Adhesive composition and adhesive film |
| JP2015074706A (en) * | 2013-10-08 | 2015-04-20 | 日立化成株式会社 | Adhesive resin composition and adhesive material |
| FR3037961B1 (en) | 2015-06-26 | 2019-12-20 | Arkema France | PEBA FOR DIRECT ADHESION ON TPE |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4419494A (en) * | 1982-03-16 | 1983-12-06 | National Starch And Chemical Corporation | Heat resistant hot melt adhesives |
| DE3305724A1 (en) * | 1983-02-18 | 1984-08-23 | Gebrüder Kömmerling Kunststoffwerke GmbH, 6780 Pirmasens | ADHESIVES AND THEIR USE |
-
1984
- 1984-10-16 FR FR8415845A patent/FR2571733B1/en not_active Expired
-
1985
- 1985-10-01 DE DE8585401916T patent/DE3567223D1/en not_active Expired
- 1985-10-01 EP EP85401916A patent/EP0179700B1/en not_active Expired
- 1985-10-15 DK DK470585A patent/DK160884C/en active
- 1985-10-15 FI FI854010A patent/FI80902C/en not_active IP Right Cessation
- 1985-10-15 JP JP60227961A patent/JPS61108676A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2571733A1 (en) | 1986-04-18 |
| FI854010A0 (en) | 1985-10-15 |
| EP0179700A1 (en) | 1986-04-30 |
| DE3567223D1 (en) | 1989-02-09 |
| EP0179700B1 (en) | 1989-01-04 |
| FR2571733B1 (en) | 1987-02-06 |
| DK160884C (en) | 1991-10-21 |
| DK470585D0 (en) | 1985-10-15 |
| FI854010L (en) | 1986-04-17 |
| FI80902C (en) | 1990-08-10 |
| DK470585A (en) | 1986-04-17 |
| JPS61108676A (en) | 1986-05-27 |
| FI80902B (en) | 1990-04-30 |
| JPH0380827B2 (en) | 1991-12-26 |
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