DE102008032573A1 - Use of an adhesive foil containing an adhesive mass equipped carrier foil on one sided for sealing microtiter plates, where the adhesive mass comprises a vinylaromatic block copolymer and an adhesive resin - Google Patents

Abstract

Use of an adhesive foil containing an adhesive mass equipped carrier foil on one sided for sealing microtiter plates, is claimed, where the adhesive mass comprises at least 50 wt.% of a vinylaromatic block copolymer and at least one adhesive resin.

Description

The The present invention relates to the use of an adhesive sheet with a carrier film equipped on one side with an adhesive for covering microtiter plates.

microtiter plates are widely used in bioanalytical processes for a multiple, fast analysis with low sample volume. typically, These microtiter plates consist of a plastic plate, the several, mutually isolated depressions in rows and columns contains, which serve as reaction vessels. There are 96-well plates, each with a volume of about 0.2 to 0.4 ml, but also those with significantly more and for that smaller depressions.

For the storage and maturation of different biological processes these individual wells must be completed, so that no liquid can be lost, but also no exchange between the individual wells can take place.

To For this purpose, single-sided adhesive films are used.

These Adhesive films must have sufficient adhesive power, on the other hand, the films have to adhere well enough also be as little permeable to water vapor as possible, to lose water during the maturation period. moreover should the adhesive films after application again without ground residues be removable and as transparent as possible, too to allow optical analysis methods.

moreover the adhesives on the adhesive films should have a certain heat resistance otherwise, during the maturation processes at high temperatures of almost 100 ° C easily folds in the Foil arise that can cause some of the wells, especially those in the corners, are open.

at A low tack of the adhesive films makes it easier especially with latex gloves, as they usually do be carried in the bioanalytical laboratories to process.

One new method for using the microtiter plates is the PCR (PCR = polymerase chain reaction). The PCR is considered a revolutionary method in biochemistry and is very can be used in a variety of ways, for example for the detection of Diseases and the development of drugs (drug detection, detection of side reactions).

at The advanced real-time PCR will be the reaction during the duplication is monitored by means of fluorescent markers.

At A Real Time PCR Analyzer Closure Film will be additional Requirements, in addition to the tightness of the reaction chambers, a high transmission and a low shrinkage of the film, the means low wrinkling during the temperature cycle.

It are different adhesive for adhesive films that are in the applications mentioned, are used, especially Advantageously, adhesives based on certain silicones have been shown.

US 6,703,120 describes such silicone-based adhesives for this application. These adhesives have the advantage of ensuring good processability because of the very low tack. In addition, they have a high bond strength, so that the liquid loss due to evaporation after 2 weeks storage is only about 1%.

adversely In particular, the high price for silicone adhesives must be paid, and the difficulty of finding a suitable protective liner because only release films or papers with fluorosilicone sufficient Enable separation.

adhesives with acrylates usually show too high a permeability for water vapor, making the loss of water too high are.

The object of the present invention is to provide an adhesive film with an adhesive which, for its part, is outstandingly suitable for sealing reaction vessels, in particular microtiter plates, and which does not or does not have the disadvantages of the known adhesives or films has a large scale.

Solved This object is achieved by the use of the invention an adhesive film, as laid down in the main claim. object The dependent claims are advantageous embodiments and developments of the adhesive film.

Accordingly, the invention the use of an adhesive film with a one-sided equipped with an adhesive backing sheet for covering microtiter plates, wherein the adhesive at least to 50 wt .-% based on the total adhesive a Vinylaromatenblockcopolymer and at least one adhesive resin.

adhesives with a high elastomer content show a sufficiently high bond strength to in use in an adhesive film used for microtiter coverage is used to achieve an evaporation rate of less than 1%. In addition, these adhesives are excellent again peel off, without adhesive residue on to leave the microtiter plates. Also when piercing with a syringe will not stick to it.

By a suitable choice of the added adhesive resins are also adhesives possible, which are transparent and colorless, so that one optical analysis of the samples or a fluorescence measurement not be disturbed.

The Adhesives are also resistant to certain in the chemicals used, especially against polar solvents such as DMSO (dimethyl sulfoxide).

Surprisingly Thus, it was found that the use of the inventive Adhesives led to adhesive foils which are very good for a microtiter cover are suitable, in particular for the use in the PCR

in the Contrary to the silicone rubber compounds can about it in addition, the adhesives based on vinylaromatic block copolymers with a normal siliconized release medium like a paper or a film, a fluorosilicone liner is not necessary.

When Adhesives are preferably those based on block copolymers containing polymer blocks predominantly formed of vinyl aromatics (A blocks), preferably styrene, and such predominantly formed by polymerization of 1,3-dienes (B blocks), preferably butadiene and isoprene or containing a copolymer of both application. It can also mixtures of different Block copolymers are used. Even products that partially, are selectively or fully hydrogenated be used. Block copolymers can be a linear Have A-B-A structure. It is also possible to use block copolymers of radial shape as well as star-shaped and linear multiblock copolymers. As further components, A-B two-block copolymers to be available.

The Pressure-sensitive adhesive preferably has a proportion of 50 to 90% by weight. vinyl aromatic block copolymer, preferably 30 to 60% by weight, and particularly preferably 55 to 70 wt .-%, each based on the entire adhesive.

When Tackifiers use adhesives according to the invention as the main component in particular adhesive resins, which with the elastomer block vinyl aromatic block copolymers are compatible.

Non-hydrogenated, partially or completely hydrogenated resins based on rosin and rosin derivatives, hydrogenated polymers of dicyclopentadiene, non-hydrogenated, partially, selectively or completely hydrogenated hydrocarbon resins based on C ₅ , C ₅ / C ₉ or are preferably suitable, inter alia C ₉ monomer streams, polyterpene resins based on α-pinene and / or β-pinene and / or δ-limonene, hydrogenated polymers of preferably pure C ₈ and C ₉ aromatics. The aforementioned adhesive resins can be used both alone and in admixture.

For use in the PCR, especially those resins are used which are particularly colorless, ideally hydrogenated hydrocarbon resins based on C ₅ -, C ₅ / C ₉ - or C ₉ .

• • primäre Antioxidantien wie zum Beispiel sterisch gehinderte Phenole
• • sekundäre Antioxidantien wie zum Beispiel Phosphite oder Thioether
• • Prozessstabilisatoren wie zum Beispiel C-Radikalfänger
• • Lichtschutzmittel wie zum Beispiel UV-Absorber oder sterisch gehinderte Amine
• • Verarbeitungshilfsmittel
• • Endblockverstärkerharze
• • Füllstoffe wie zum Beispiel Siliziumdioxid, Glas (gemahlen oder in Form von Kugeln), Aluminiumoxide, Zinkoxide, Calciumcarbonate, Titandioxide, Ruße, etc. ebenso wie Farbpigmente und Farbstoffe sowie optische Aufheller
• • gegebenenfalls weitere Polymere von bevorzugt elastomerer Natur; entsprechend nutzbare Elastomere beinhalten unter anderem solche auf Basis reiner Kohlenwasserstoffe, zum Beispiel ungesättigte Polydiene wie natürliches oder synthetisch erzeugtes Polyisopren oder Polybutadien, chemisch im Wesentlichen gesättigte Elastomere wie zum Beispiel gesättigte Ethylen-Propylen-Copolymere, α-Olefincopolymere, Polyisobutylen, Butylkautschuk, Ethylen-Propylenkautschuk sowie chemisch funktionalisierte Kohlenwasserstoffe wie zum Beispiel halogenhaltige, acrylathaltige oder vinyletherhaltige Polyolefine, um nur einige wenige zu nennen

As further additives can typically be used:

• • primary antioxidants such as sterically hindered phenols
• • secondary antioxidants such as phosphites or thioethers
• • Process stabilizers such as C radical scavenger
• • Sunscreens such as UV absorbers or hindered amines
• • processing aids
• • End block amplifier resins
• • Fillers such as silicon dioxide, glass (ground or in the form of spheres), aluminum oxides, zinc oxides, calcium carbonates, titanium dioxides, carbon blacks, etc., as well as pigments and dyes and optical brighteners
• Optionally further polymers of preferably elastomeric nature; suitably usable elastomers include those based on pure hydrocarbons, for example unsaturated polydienes such as natural or synthetically produced polyisoprene or polybutadiene, chemically substantially saturated elastomers such as saturated ethylene-propylene copolymers, α-olefin copolymers, polyisobutylene, butyl rubber, ethylene Propylene rubber and chemically functionalized hydrocarbons such as halogen-containing, acrylate-containing or vinyl ether-containing polyolefins, to name but a few

The Adhesive compositions of the invention show a particular good adhesion to polypropylene and polystyrene, the materials made usually the microtiter plates are produced.

By the high proportion of block copolymer softens the block copolymer masses not at relatively moderate temperatures, but survive also unchanged the usual processes with the microtiter plates are performed, such as heating at 90 ° C and stored at -40 ° C.

Of the Carrier of the adhesive film is typically dependent from the requirement of breaking strength and transparency made of polypropylene or polyethylene terephthalate. But also applications with an aluminum foil as a carrier or an aluminum-coated film conceivable.

Preferably both adhesive and carrier film are transparent, in such a way that the transparent adhesive film is preferably has a transmission of greater than 60%, in particular a transmission greater than 90% at one wavelength from 350 to 1150 nm.

With the transmittance - sometimes only briefly as transmission - which is usually given in% the ratio of on the back of a with Light irradiated the body's incoming light output meant to the incident on the front light output. The transmission is trimmed by reflection and absorption.

It Thus, the following applies: transmittance = (1 - reflectance) × (1 - absorptance).

in the The invention will be more closely understood by way of examples explains without thereby limiting the invention in any way to want.

Examples

The Production and processing of the PSAs can both consist of the solution, as well as from the melt. Especially However, preference is given to the production of the PSAs from the solution, to prevent too early networking.

Production of the patterns:

The Ingredients are in a mixture of toluene and gasoline 50:50 dissolved, so that a solids content of 40 wt .-% is formed. The samples are then placed on a 23 μm thick PET film so spread and dried at 100 ° C that a basis weight of 50 g / cm adhesive remains.

all Examples are used as anti-aging agent 0.5 parts Irganox 1010 and 0.5 part Tinuvin P added as UV absorber.

• Angaben jeweils in Gewichtsanteilen

Eigenschaften der eingesetzten Rohstoffe: Kraton D 1165 SIS, ca. 16 Gew.-% Zweiblock, Blockpolystyrolgehalt: 30 Gew.-%, Kraton Polymers Kraton D 1118 SBS, ca. 76 Gew.-% Zweiblock, Blockpolystyrolgehalt: 31 Gew.-%, Kraton Polymers Kraton D 1101 SBS, ca. 18 Gew.-% Zweiblock, Blockpolystyrolgehalt: 31 Gew.-%, Kraton Polymers Solprene S 411 radiales SBS, ca. 8 Gew.-% Zweiblock, Blockpolystyrolgehalt: 30 Gew.-%, Dynasol Foral 85 hydrierter Kolophoniumester, Erweichungspunkt (Ring & Ball) ca. 85°C, Eastman Escorez 5690 hydriertes Kohlenwasserstoffharz auf C₅-/C₉-Basis, Erweichungspunkt (Ring & Ball) ca. 90°C, Exxon Mobile Wingtack 10 flüssiges Kohlenwasserstoffharz, Goodyear Shellflex 371 naphthenisches Öl, Shell Kristalex 1140 reines Aromatenharz als Endblockverstärker mit einem Erweichungspunkt von ca. 140°C, Eastman Irganox 1010 sterisch gehindertes Phenol, Ciba Additive Tinuvin P UV-Absorber, Ciba Additive Composition of the examples see Table 1. Table 1: 1 2 3 4 5 C6 Kraton D 1165 50 Kraton D 1118 50 33 20 40 33 Kraton D 1101 67 100 70 60 67 Solprene S 411 10 Foral 85 60 Escorez 5690 50 45 50 40 120 Wingtack 10 7 10 5 10 Shellflex 371 8th 20 Kristalex 1140 20

• In each case in parts by weight

Properties of the raw materials used: Kraton D 1165 SIS, about 16% by weight diblock, block polystyrene content: 30% by weight, Kraton Polymers Kraton D 1118 SBS, about 76% by weight diblock, block polystyrene content: 31% by weight, Kraton Polymers Kraton D 1101 SBS, about 18% by weight diblock, block polystyrene content: 31% by weight, Kraton Polymers Solprene S 411 radial SBS, about 8% by weight diblock, block polystyrene content: 30 Wt%, Dynasol Foral 85 hydrogenated rosin ester, softening point (ring & ball) approx. 85 ° C, Eastman Escorez 5690 hydrogenated hydrocarbon resin based on C ₅ - / C ₉ , Softening point (ring & ball) about 90 ° C, Exxon Mobile Wingtack 10 liquid hydrocarbon resin, Goodyear Shellflex 371 naphthenic oil, shell Kristalex 1140 pure aromatic resin as Endblockverstärker with a Softening point of about 140 ° C, Eastman Irganox 1010 hindered phenol, Ciba additives Tinuvin P UV absorber, Ciba additives

bond strength

The Testing of the peel strength (bond strength) was carried out according to PSTC-1.

One 2 cm wide strip of a sample prepared as described above was passed through on a steel plate or polystyrene plate three times double rolling over with a 2 kg roller bonded. The plate was clamped and the pressure-sensitive adhesive strip over its free end on a tensile testing machine under a peel angle subtracted from 180 ° at a speed of 300 mm / min.

ullages

All 96 wells of a microtiter plate were each filled with 50 μl of a colored aqueous solution filled. The surface of the plate was rubbed dry with a lint-free cloth to remove adherent liquid drops.

The Plate was then with the adhesive film of the invention closed by placing it in the center of the plate and with a customary applicator all around was pressed well. The weight of the plate was up the analytical balance determined.

• 1: 94°C 2 min
• 2: 94°C 15 s
• 3: 50°C 15 s
• 4: 72°C 30 s
• 5: 72°C 2 min

wobei die Schritte 2 bis 4 30 mal wiederholt wurden. Anschließend wurde auf 22°C temperiert. Nach einer visuellen Kontrolle, ob alle Vertiefungen noch gefüllt waren, wurden die Muster nach 24 h erneut gewogen. Die Verdunstung wurde daraufhin in Prozent ausgerechnet.There was a temperature program driven by

• 1: 94 ° C 2 min
• 2: 94 ° C 15 s
• 3: 50 ° C 15 s
• 4: 72 ° C 30 s
• 5: 72 ° C 2 min

wherein steps 2 to 4 were repeated 30 times. It was then heated to 22 ° C. After a visual check that all wells were still full, the samples were re-weighed after 24 hours. The evaporation was then calculated in percent.

Peel off after storage

The glued patterns from the previous test were after cooling slowly drawn off to room temperature by hand. It was on Masserückstände paid attention to the microtiter plate.

Resistance to DMSO

Instead of the colored aqueous solution became a solution of 5 wt .-% DMSO used in water, the microtiter plates More often kept upside down to a wetting of the adhesive tape with the DMSO solution.

Examines was, whether the tapes changed, for Swell example.

transparency

It became the transparency of the finished products after ASTM-D 1003-61 , Method A measured.

softening

The softening point was determined by the ring and ball method, the usual method for determining softening points. Details can be ASTM E 28 and the DIN EN 1238 are taken, which is hereby incorporated by reference.

In the case of the exemplary adhesive films, the following adhesive technical data were determined: Pressure Sensitive Adhesive Example No. Adhesive steel immediately in N / cm Adhesive strength polystyrene immediately in N / cm Remove after 90 ° C storage for 1 week Fluid losses after storage in% by weight Resistance to DMSO 1 3.6 2.7 No Residues 1.5 OK 2 5.2 4.7 No Residues 1.2 OK 3 4.1 3.6 No Residues 0.9 OK C4 3.9 2.5 Bulk threads residues 5.3 Some reaction vessels open OK

As can be seen, there are no residues on the microtiter plate for the high vinyl aromatic block copolymer. Although here the bond strengths are significantly lower, it comes also not to detach the adhesive films, which is visible in the low evaporation values.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• US 6703120 [0012]

Cited non-patent literature

• ASTM-D 1003-61 [0048]
• ASTM E 28 [0049]
• - DIN EN 1238 [0049]

Claims (7)

Use an adhesive film with a one-sided equipped with an adhesive backing sheet for covering microtiter plates, wherein the adhesive at least to 50 wt .-% based on the total adhesive a Vinylaromatenblockcopolymer and at least one adhesive resin. Use according to claim 1, characterized the adhesive comprises a proportion of 50 to 90% by weight, preferably from 30 to 60 weight percent, more preferably from 55 to 70 weight percent vinyl aromatic block copolymer contains based on the total adhesive. Use according to claim 1 or 2, characterized that the vinylaromatic block copolymers are styrenic block copolymers is. Use according to at least one of the claims 1 to 3, characterized in that the adhesive further elastomers contains. Use according to at least one of the preceding Claims, characterized in that the block copolymers at least partially hydrogenated. Use according to at least one of the preceding claims, characterized in that hydrogenated hydrocarbon resins based on C ₅ -, C ₅ / C ₉ or C ₉ are used as tackifier resins. Use according to at least one of the preceding Claims, characterized in that the carrier film a polypropylene, a polyethylene terephthalate or an aluminum foil or an aluminum-coated film.