JP2002544320A - Silicone adhesives, products, and methods - Google Patents

Abstract

  (57) [Summary] The present invention provides silicone-based adhesives, preferably pressure-sensitive adhesives, adhesive products, and methods. Preferably, the product is a cover tape for an analytical container such as, for example, a microtiter plate, a microfluidic device, and a continuous multiple reservoir carrier, or other analytical container or biosensor. Typically, such analytical vessels are used in biological analysis applications and are designed to contain solids and fluids, including, for example, liquids, gases, powders, and gels that may contain biological samples or organic solvents. Is done.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The invention relates to silicone adhesives, products, and methods of making and using. The adhesive may be used in analytical containers such as microtiter plates, microfluidic devices, discrete or continuous multiple reservoir carriers, or other fluids such as those specifically designed to hold various liquids for biological analysis applications, for example. Particularly useful in cover tapes for products such as analytical vessels.

BACKGROUND Microtiter plates used in the handling of liquid materials in a number of biological assays for rapid low volume analysis are well known. Typical screening techniques combine an assay plate with multiple wells or wells with a liquid handling device to provide a rapid automated analysis system. In the current standard analysis system, each assay plate has a capacity of 96 wells,
Each well is addressable by a suitably programmed device. The volume of each of the 96 wells is from about 0.2 ml to about 0.4 ml. Smaller volume wells result in an assay plate with more sample capacity. For example, assay plates containing 1536 wells, each volume of less than 5 μl are known. These plates with increased sample capacity can be used for enzyme assays,
It has demonstrated utility in a variety of assays, including receptor-binding group assays, as well as cell-based assays. The increasing number of sample wells per assay plate requires the accuracy of the instruments involved in analysis using these assay plates.

[0003] Liquid handling for biological analysis applications using either 96-well, 384-well, or 1536-well assay plates requires batch operation with speed limitations due to assay tray loading and positioning. Can also be considered. A possible improvement in the rate of sample analysis results from the use of a continuous strip material with sample wells shaped along its length. U.S. Pat. No. 4,883,642 (Bisconte) proposes such a strip or tape. This patent teaches a continuous ribbon that may be smooth or suitably shaped to incorporate multiple microwells. The analysis of fixed biological samples uses a smooth continuous ribbon version, while the microwell ribbons are useful for analyzing living biological samples. The two tracks located along the opposite ends of the ribbon provide an addressable means of moving and positioning the ribbon to the exact position selected with an adjustment accuracy of 10 μm. The tracks may be encoded using, for example, magnetic, optical, or computerized methods that allow the ribbon to be manipulated and positioned. Metering syringe-type devices placed using a step-by-step motor distribute a biological sample within a microwell.

[0004] This continuous multiple reservoir carrier is useful in automated analysis of biological samples such as histological sections. An adhesive film may be used to protect the sample, whether applied to a smooth ribbon or included in a microwell. The adhesive film covers the smooth film surface or seals the individual microwell openings. It may or may not be breathable.

US Pat. No. 5,721,136 (Finney et al.) Teaches the use of a multilayer sheet having a silicone adhesive thereon for use on a biochemical reaction vessel. One layer provides strength and integrity for the film. The second layer is a thick, deformable material having a very low tack surface in the range of 2 mils to about 40 mils (50 μm to 1016 μm). The elasticity of the second layer results in a good seal when tightened during thermal cycling. Rubbery materials also provide very low levels of adhesion. The sheet peeling force from the polypropylene surface is 0.11 N / dm to 0.5
It is reported to be in the range of N / dm (0.1 oz-in to 4.5 oz / in).
To prevent the tape from adhering to rubber gloves commonly used in biological research, a low tack adhesive tape is desirable, but when applied to microplates, for example, the low adhesion of a thick elastic adhesive tape The properties tend to cause high evaporation rates and increase the incidence of cross-contamination during storage and handling.

[0006] Silicones may be cured or cross-linked at elevated temperatures with a catalyst such as a peroxide or metal salt to increase cohesion and reduce contamination by residual adhesive.
For example, benzoyl peroxide requires a curing temperature above 150 ° C. for the catalyst to work. Thus, backing materials having a low melting or softening point, such as polyethylene films, may be stretched excessively or distorted in size during curing. One convention for preparing curable silicone tapes is to coat the curable silicone with a release liner consisting of a fluorosilicone coating and a PET (polyethylene terephthalate) backing. The tape is then laminated to a backing material having a lower melting or softening point temperature. Since release liners are commonly used to process and protect silicone adhesive surfaces, the release force that separates the tape from the release liner is kept low, especially when the release liner is removed during automated processing. It is important to minimize material distortion.

[0007] US Patent No. 5,082,706 (Tangney) has a release force from the fluorosilicone release layer of less than 7.7 N / dm (7 oz / in) and a peel adhesion of at least 46. A 4 N / dm (42.2 oz / in) silicone PSA / fluorosilicone release laminate is described. The adhesive includes a tackifying resin (often referred to as MQ resin) containing two structural units, one of which is R ₃ SiO _1/2 (often referred to as M). And the other is SiO _4/2 (often referred to as Q). The Handbook of
Pressure-Adhesive Technology, 2nd edition (D.
(Satas, 1989), page 510, the peel strength of the silicone pressure sensitive adhesive can be adjusted by adjusting the amount of tackifying resin. For example, by increasing the amount of the tackifier resin, the peeling adhesive force increases.
Typically, however, there is a point at which peel adhesion is maximized. Therefore, increasing the amount of tackifier resin beyond this point can cause a decrease in peel adhesion.

What is needed is a good release from a release liner while providing effective peel strength from adhesives and adhesive products, particularly the materials that typically form the analytical container. A cover tape for an analysis container, preferably sufficiently low tack suitable for use with the analysis container. It is particularly desirable if such an adhesive is substantially resistant to liquids, especially organic solvents such as dimethyl sulfoxide, which are frequently used in biological analysis applications.

The present invention provides an adhesive, preferably a pressure sensitive adhesive (PSA), an adhesive product, and a method. Preferably, the product is a cover tape for an analytical container such as, for example, a microtiter plate, a microfluidic device, and a continuous multiple reservoir carrier, or other analytical container or biosensor. Typically, such analytical vessels are used in biological analytical applications, such as to contain solids and fluids, including liquids, gases, powders, and gels, which may include biological samples or organic solvents. Designed.

In a preferred embodiment, the cover tape for such an analysis container is a container closure, in which each reservoir, for example a well or channel, holds the contents and / or reduces the evaporation and contamination of the contents. Provide a sealed membrane to be part of the Preferred cover tapes have sufficient transparency to allow for photometric analysis and / or visual inspection, for example, dimethyl sulfoxide (DMSO),
It is substantially resistant to solvents commonly used in biological analysis applications, such as water, acetonitrile / water, methanol, ethanol, or mixtures thereof.
For use herein, a substantially solvent resistant cover tape, and especially an adhesive,
It does not substantially swell or dissolve in a solvent used in a specific application, and retains sufficient adhesion to an analysis container.

In one embodiment, the present invention provides a compound represented by the general formula: R ¹ R ₂ SiO (R ₂ SiO) _n SiR ₂ R ¹ wherein each R is independently a monovalent hydrocarbon group. And each R ¹ is independently an alkenyl group, and n is an integer.), And a polydiorganosiloxane having a number average molecular weight of at least 20,000; (b) a general formula: R ¹ R ₂ SiO (R ₂ SiO ) _m (in R ¹ RSiO) _n SiR ₂ R ¹ (wherein each R and R ¹ are independently a monovalent hydrocarbon group, at least two R ¹ groups are alkenyl groups, m and n are And the sum is an integer that provides an alkenyl equivalent of from about 250 to about 10,000.), And a polydiorganosiloxane having a number average molecular weight of less than 20,000; (c) (R ² ) ₃ SiO _1/2 units (in the formula, each R ² is independently an alkyl group, Al It is selected from the group of alkenyl groups or hydroxyl groups, 95 mole% of at least all R ² groups
Is a methyl group. ) And an SiO ₂ unit in a molar ratio in the range of 0.6: 1 to 1: 1; and (d) 1 to 40 alkenyl groups in the components (a) to (c). (E) an aliphatic unsaturation-free organohydrogenpolysiloxane having an average of at least two silicon-bonded hydrogen atoms in each molecule in an amount sufficient to provide the silicon-bonded hydrogen atoms of 0.1 parts by weight per 1 million parts by weight of the total of the components (a) to (d)
A silicone adhesive, preferably a pressure sensitive adhesive, is prepared from a component comprising a sufficient amount of a Group VIIIB containing catalyst to provide 〜1,000 parts by weight of a Group VIIIB metal. Methods of making and using such adhesives are also provided.

In another embodiment, the present invention provides an adhesive product comprising a substrate having on at least one major surface thereof a silicone-based adhesive, preferably a pressure sensitive adhesive of the above formula. Adhesive products include tapes, labels, and other sheets that are useful in a variety of ways, including medical, graphic, and analytical applications.

In yet another embodiment, the present invention provides an assay container comprising a surface, preferably having at least one reservoir therein, and a cover tape adhered to the surface, wherein the cover tape comprises a backing tape. And an adhesive of the above formula disposed on at least one major surface of the backing material and in contact with the container surface.

[0014] In yet another embodiment, the invention provides an analysis container comprising a surface comprising polypropylene, polystyrene, or a combination thereof, and a cover tape adhered to the surface, wherein the cover tape comprises a backing material. And an adhesive disposed on at least one major surface of the backing material and in contact with the container surface, the adhesive comprising: (a) a general formula: R ¹ R ₂ SiO (R ₂ SiO) _n SiR ₂ R ¹ (Wherein each R is independently a monovalent hydrocarbon group, each R ¹ is independently an alkenyl group, and n is an integer), (b) (R ² ) ₃ SiO _1/2 units, wherein each R ² is independently selected from the group of alkyl, alkenyl, or hydroxyl groups, at least 95 mole percent of all R ² groups
Is a methyl group. ) And SiO ₂ units from 0.6: 1 to 1: Organopolysiloxane MQ resin containing a molar ratio of 1 range, (c) if present, alkenyl in component (a) and component (b) Aliphatic unsaturation-free organohydrogenpolysiloxane having an average of at least two silicon-bonded hydrogen atoms in each molecule in an amount sufficient to provide from 1 to 40 silicon-bonded hydrogen atoms per group Siloxane, (d) 0.1 parts by weight of 1,000,000 parts by weight of the total amount of components (a) to (c)
And a sufficient amount of a Group VIIIB-containing catalyst to provide １，1,000 parts by weight of a Group VIIIB metal.

In yet another embodiment, the invention provides an assay container comprising a surface and a cover tape adhered to the surface, wherein the cover tape has a backing material and at least one major surface of the backing material. An adhesive disposed in contact with the surface of the container, the adhesive comprising: (a) a general formula: R ¹ R ₂ SiO (R ₂ SiO) _n SiR ₂ R ¹ wherein each R is independently monovalent Wherein each R ¹ is independently an alkenyl group, and n is an integer.) (B) (R ² ) ₃ SiO _1/2 units (wherein each R ² is independently selected from the group of alkyl, alkenyl, or hydroxyl groups, at least 95 mole% of all R ² groups
Is a methyl group. ) And SiO ₂ units from 0.6: 1 to 1: Organopolysiloxane MQ resin containing a molar ratio of 1 range, (c) if present, alkenyl in component (a) and component (b) Aliphatic unsaturation-free organohydrogenpolysiloxane having an average of at least two silicon-bonded hydrogen atoms in each molecule in an amount sufficient to provide from 1 to 40 silicon-bonded hydrogen atoms per group Siloxane, and (d) 0.1 parts by weight of 1,000,000 parts by weight of the total amount of the components (a) to (c).
A VIIIB-containing catalyst in an amount sufficient to provide 〜1,000 parts by weight of a Group VIIIB metal, prepared from components comprising: a fluorosilicone-coated polyethylene terephthalate release liner;
And 0.8 g / 154.8 c on the propylene / ethylene copolymer backing material
When placed at m ² to form a laminate and adhered to a glass plate, it exhibits a 180 ° peel force of less than about 20 N / dm when measured at room temperature at 30.5 cm / min.

The analysis vessel can be in the form of a substantially continuous tape, or it can be of discrete shape and size, preferably with one or more reservoirs.
For example, the analysis vessel may be a microtiter plate, a microfluidic device comprising a substrate and one or more channels therein, or a plurality of reservoirs at predetermined intervals (preferably evenly spaced) along its length. Can be in the form of a substantially continuous polymer strip (ie, tape). Thus, the reservoir (s) can be of a wide variety of shapes and dimensions. Preferably they form a well or a channel.

The adhesive of the present invention can form a pattern on a substrate (eg, a backing material of a cover tape), or it can form a continuous layer on at least one major surface thereof. It preferably adheres, typically using pressure, unlike a heat activated adhesive,
A pressure-sensitive adhesive that does not require the use of a heating device. Certain preferred tapes of the present invention can be conveniently repositioned at different locations if desired, or can be relocated at the same location for resealing.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to silicone-based adhesives, preferably pressure-sensitive adhesives, products (such as tapes) on which such adhesives are placed, and such adhesives and products. And a method for producing and using the same. One particularly preferred product is a cover tape for an analysis container. As used herein, an analysis vessel is a device that receives a sample, reagent, or solvent. Preferably, the device is configured to receive a fixed volume of sample, reagent, or solvent, most preferably a very small volume. Such a preferred configuration includes one or more reservoirs. Examples include discontinuous or continuous (eg, strip or tape) structures containing assay plate arrays (eg, microtiter plates) and multiple wells, channels, or other reservoirs. Preferred assay vessels provide an open system (eg, a well or channel) of one or more reservoirs to which fluid may be added directly without further modification. Open systems require careful control of evaporation and cross-contamination which limits their practical use. Thus, cover tapes are desirable which provide a closed system that does not necessarily require special sample transport and containment.

A cover tape is applied along the length and width of the analytical container and the container, preferably the reservoir (s) of the container, is sealed. Preferably this results in the production of a separate closed container. The material can be added if desired, e.g., using a suitable hypodermic needle.
It may be injected through the cover tape into a closed reservoir, or may be withdrawn therefrom. Preferred analysis vessels can include one or more reservoirs. They can be substantially continuous or discrete (ie, discontinuous) structures. For example, the analysis vessel can be in the form of a microtiter plate, conventionally used in biological analysis methods. Alternatively, it can be a microfluidic device or a continuous multi-reservoir carrier, for example, which can be cut into individual (discontinuous) pieces if desired. Preferably, conventional analysis vessels are made of, for example, polyolefin, polystyrene, and / or polycarbonate, and more preferably, polypropylene and / or polystyrene.

[0020] The cover tape of the present invention, acting as a sealing membrane, comprises a silicone adhesive, preferably a pressure sensitive silicone adhesive, disposed on a backing material. Preferably, the backing is made of a transparent material to allow photometric analysis and / or visual inspection. The cover tape of the present invention is preferably made of a material from which a conventional analytical container is made (
Preferably adheres well to polyolefin, polystyrene, polycarbonate, or combinations thereof, and more preferably, polypropylene, polystyrene, or combinations thereof, but is preferably repositionable (ie, on the backing of the adhesive product) The adhesive allows a cycle of alternating material being bonded onto it and then removed while the adhesive is held permanently), but does not allow for cross-contamination of the sample material within the individual reservoirs. Preferably, the cover tape provides an effective seal against sample evaporation while retaining adhesion during high and low temperature storage (e.g., about -80 <0> C to about 200 <0> C) (e.g., in an analytical quantitative analysis environment). Less than 5% loss within 24 hours of use). A suitable cover tape of the present invention is:
For example, a cover tape that allows puncturing with a needle, such as a stainless needle or a plastic sampling pipette tip, but that resists puncturing, may also be used.
These puncture sites may or may not reclose. The ability to be punctured and reclosed is typically controlled by the choice of backing material and / or adhesive thickness (eg, a 0.01 cm thick adhesive layer is sufficient to reclose the puncture site. May flow to).

The choice of adhesive is particularly important, as the use of a cover tape allows the adhesive to be exposed to the fluid content of the reservoir. Thus, cover tapes, and especially adhesive compositions, are commonly used in dimethyl sulfoxide (DM
It is important that they do not substantially dissolve in or otherwise react with solvents such as SO) and acetonitrile / water. Therefore, a preferred adhesive is DM
It is substantially resistant to a wide variety of solvents such as SO, water, acetonitrile / water, methanol, ethanol, or similar polar solvents, as well as mixtures thereof. That is, preferred adhesives do not substantially swell or dissolve in solvents used for particular applications, while retaining sufficient adhesion to the analytical container.

Further preferred adhesives have sufficient cohesion to leave almost no residue on the analysis container or needle or pipette tip after withdrawal from the puncture hole in the cover tape.
Or a pressure-sensitive adhesive that does not leave at all. The adhesive also preferably exhibits low tack and helps reduce the adhesion of the cover tape to commonly used rubber gloves made of latex or nitrile rubber (eg, a peel force of about 10 N / dm.
Less than).

Preferred adhesives are also substantially biocompatible (ie, substantially physiologically inert). As used herein, a “biocompatible” material generally refers to a significant adverse reaction (eg, tissue death, tumor formation, allergic reaction, inflammatory response, or blood clotting) upon contact with bodily fluids and / or tissue. Toxic or antigenic reaction).

The adhesives of the present invention typically have excellent thermal and oxidative stability and from about -80 ° C.
It includes silicones having a very wide working temperature range of about 200 ° C. (ie, the temperature range in which adhesives are useful). Silicones are also generally inert to a wide variety of polar chemicals and solvents commonly used in biological assays, such as water, methanol, ethanol, acetonitrile / water, and DMSO. Further, silicone is substantially biocompatible and is used in a variety of medical devices. These properties make them excellent adhesives for use in cover tapes for analysis vessels used, for example, in biological analysis applications. However, not all silicone adhesives in combination with all backing materials have the right balance of properties (eg, peel force, peel force, and tack).

The silicone adhesive laminate disclosed in US Pat. No. 5,082,706 (Tangney) includes an addition cured silicone pressure sensitive adhesive on an addition cured fluorosilicone release coating. When a thin backing material is used in the adhesive product structure, the release force is low enough to separate the adhesive product (eg, cover tape) from the release liner, even if permanent deformation of the backing material occurs. Desirably small. Thin backing materials (eg, less than about 0.005 cm thick) and / or backing materials having low flexural modulus (eg, polyolefins) are easily deformed. Thus, the peel force required to separate such an adhesive product based on a backing material needs to be very low to avoid inducing permanent deformation or curl in the adhesive product. .

After the adhesive has been cast onto the release coating and cured while in contact therewith, the adhesive necessary to separate it from the fluorosilicone release coating of US Pat. No. 5,082,706 (Tangney) is required. The peel force is reported to have a value of less than 200 g per inch (7.7 N / dm), and a stable subsequent bond strength (46.4 N / dm for stainless steel) and a stable subsequent tack at the same time Although shown, commercially available materials generally do not exhibit sufficiently low peel forces for many applications. For example, Dow Corning 7657 silicone adhesive exhibits a release force of 7.1 N / dm from a Rexam CLPET-6J / 000 transition liner (a fluorosilicone coating on a polyethylene terephthalate backing available from Rexam Release Corp., Bedford, Ill.). (See Example 1 for curing conditions). While this may be appropriate for some applications, it is typically not suitable for adhesive transfer to very thin and / or brittle backings or in automated systems where the release liner is removed. Thus, for such applications, compositions that provide lower release values (eg, about 5 N / dm or less) are particularly desirable.

The silicone adhesive of US Pat. No. 5,082,706 has the following general formula: (a) R ¹ R ₂ SiO (R ₂ SiO) _n SiR ₂ R ¹ (where each R is independently (B) (R ² ) ₃ SiO _1/2 units (referred to as M units), wherein each R ¹ is independently an alkenyl group, and n is an integer. Wherein each R ² is independently selected from the group of an alkyl group, an alkenyl group, or a hydroxyl group;
95 mol% of at least all the R ² groups are methyl groups. ) And SiO ₂ units (often referred to as Q units) in a molar ratio in the range of 0.6: 1 to 0.9: 1 (often referred to as MQ resins) (C) if present, from 1 to 4 per alkenyl group in components (a) to (c)
An aliphatic unsaturation-free organohydrogenpolysiloxane having an average of at least two silicon-bonded hydrogen atoms in each molecule in an amount sufficient to provide zero silicon-bonded hydrogen atoms; and d) 0.1 to 100 parts by weight of the total amount of components (a) to (c)
It is prepared from components containing a sufficient amount of a platinum-containing catalyst to provide 1,000 parts by weight of platinum.

In certain embodiments of the present invention, similar preferred adhesives can be used, wherein the hydrocarbon groups of the above formula are, for example, alkyl and alkenyl groups, such as groups containing up to 10 carbon atoms. The alkyl group can be methyl, ethyl, propyl, hexyl, and the like, for example, a group containing up to 10 carbon atoms,
Alkenyl groups can be, for example, vinyl, propenyl, hexenyl, etc., such as groups containing up to 10 carbon atoms, and the molar ratio of M to Q units in the MQ resin is 0.
. The range is from 6: 1 to 1: 1 and Group VIIIB contains a metal catalyst.

[0029] Embodiments of the silicone adhesive of US Pat. No. 5,082,706 containing higher levels of MQ resin may be used on other substrates, such as polyolefins, polystyrene, polycarbonate, and preferably polypropylene and polystyrene. A) typically shows a lower release value from the fluorosilicone liner without significantly adversely affecting the release value from).

Preferably, the level of the MQ resin (and other components of the adhesive described herein) is adjusted to 0.8 g / 154 on a fluorosilicone-coated polyethylene terephthalate release liner and ethylene / propylene copolymer backing. .8cm ²
When the laminate is adhered to a glass plate, the laminate is adhered to a glass plate, and when measured at room temperature (about 25 ° C. to about 30 ° C.) at 30.5 cm / min, about 20 N / dm or less, Preferably, an adhesive is provided that exhibits a 180 ° peel force of about 15 N / dm or less, even more preferably about 10 N / dm or less, and most preferably about 5 N / dm or less. Preferably, the level of the MQ resin (and other components of the adhesive described herein) is adjusted so that the polypropylene is disposed at a coverage of 0.8 g / 154.8 cm ² on the ethylene / propylene copolymer backing. Once adhered to the plate, at least about 5 N / dm, more preferably at least about 10 N / dm, measured at 30.5 cm / min at room temperature (about 25 ° C. to about 30 ° C.)
Also provided is an adhesive exhibiting a 180 ° peel force of at least about 15 N / dm, and most preferably at least about 15 N / dm. Preferably, the peel force is less than about 50 N / dm.

Suitable types and amounts of the various adhesive components described above are disclosed in US Pat.
, 082,706 (Tangney). Typically, the amount of MQ resin (ie, where R ² is an alkyl group) required to achieve the desired levels of release and release force is determined by the general formula: R ¹ R ₂ SiO (R ₂ SiO) _n SiR ₂ It depends on the amount of polydiorganosiloxane having R ¹ . The total weight (that is, parts by weight) of the MQ resin plus the polydiorganosiloxane having the general formula: R ¹ R ₂ SiO (R ₂ SiO) _n SiR ₂ R ¹ is 10
If equal to zero, preferably at least about 50 parts by weight of the MQ resin and no more than about 70 parts by weight of the MQ resin are used to achieve the desired levels of release and release force.

As an alternative to, or in addition to, increasing the MQ resin level in the silicone adhesive of US Pat. No. 5,082,706 to lower the release force level, a low molecular weight vinyl substituted siloxane is added to the composition. it can. That is, the polydiorganosiloxanes described above are actually present in the adhesives of these preferred embodiments as high and low molecular weight components. This low molecular weight component is a commercially available release modifier (eg, Dow Co.) typically used to increase release.
ringing SYL-OFF7615 release modifier or General Ele
tric Silicones SL-6030). It is therefore not expected that this material will be used to reduce the release force without significantly affecting the release force.

Such a silicone pressure-sensitive adhesive includes (a) a compound represented by the following general formula: R ¹ R ₂ SiO (R ₂ SiO) _n SiR ₂ R ¹ (wherein each R is independently a monovalent hydrocarbon group (eg, Each R ¹ is independently an alkenyl group (eg, vinyl, propenyl, hexenyl, etc. containing up to 10 carbon atoms), and n is An integer.) And a polydiorganosiloxane having a number average molecular weight of at least 20,000, (b) a general formula, R ¹ R ₂ SiO (R ₂ SiO) _m (R ¹ RSiO) _n SiR ₂ R ¹ , wherein , Each R and R ¹ is independently a monovalent hydrocarbon group (eg, an alkyl group containing up to 10 carbon atoms, an alkenyl group, etc.), and at least two R ¹ groups are alkenyl groups (eg, 10 Until Vinyl containing carbon atoms, propenyl,
Hexenyl), and m and n are integers, the sum of which is about 250 to about 1
It provides an alkenyl equivalent of 000. ) And a polydiorganosiloxane having a number average molecular weight of less than 20,000, (c) (R ² ) ₃ SiO _1/2 units (referred to as M units), wherein R ² is alkyl (
Selected from the group of, for example, methyl, ethyl, propyl, hexyl, etc. containing up to 10 carbon atoms, alkenyl (eg, vinyl, propenyl, hexenyl, etc. containing up to 10 carbon atoms), or hydroxyl groups; at least 95 mol% of R ² is a methyl group. ) And SiO ₂ units (referred to as Q units)
(MQ) in a molar ratio ranging from 0.6: 1 to 1: 1
(Referred to as resin), (d) an average amount in each molecule in components (a)-(c) in an amount sufficient to provide from 1 to 40 silicon-bonded hydrogen atoms per alkenyl group. An organohydrogenpolysiloxane free of aliphatic unsaturation having at least two silicon-bonded hydrogen atoms, and (e) a total amount of components (a) to (d) of 0.1 parts by weight per 1 million parts by weight. 1 to
It is prepared from a component comprising a sufficient amount of a Group VIIIB containing catalyst to provide 1,000 parts by weight of a Group VIIIB metal. Preferably, such compositions comprise both non-functional and functional MQ resins, especially alkenyl-functional MQ resins.

Suitable polydiorganosiloxanes having the general formula R ¹ R ₂ SiO (R ₂ SiO) _n SiR ₂ R ¹ and a number average molecular weight of at least 20,000 are available from Gelest Inc. of Tarrytown, PA. Commercially available from such suppliers. Examples are described in U.S. Pat. No. 5,082,706 (Tang).
ney). In a particularly preferred embodiment, the molecular weight is preferably at least about 50,000, more preferably at least about 100,000, and most preferably at least about 250,000.

A suitable polydiorganosiloxane having the general formula: R ¹ R ₂ SiO (R ₂ SiO) _m (R ¹ RSiO) _n SiR ₂ R ¹ and a number average molecular weight of less than 20,000 is available from Gelest Inc. Commercially available from such suppliers. Preferred such materials are (as a result of the choice of m and n) from about 250 to about 10,000, more preferably from about 250 to about 5000, and most preferably from about 250 to about 2000.
Alkenyl equivalent of

The high molecular weight polydiorganosiloxane component (ie, having a number average molecular weight of at least 20,000), based on the total weight of both high and low molecular weight polydiorganosiloxane, is preferably at least about 50 parts by weight. The low molecular weight polydiorganosiloxane component (ie, having a number average molecular weight of less than 20,000) present in the adhesive composition in an amount up to about 95 parts by weight is preferably at least about 5 parts by weight and about 50 parts by weight. Parts or less are present in the adhesive composition.

[0037] Suitable functional and non-functional MQ organopolysiloxane resins are available from General Electric Co. of Waterford, NY. Silicone Resin Division, PCR, Inc., Gainesville, Florida. And commercial sources such as Rhone-Poulenc latex and specialty polymers from Rock Hill, South Carolina. Examples are described in U.S. Pat. No. 5,082,706 (
Tangney). Such resins are generally supplied in organic solvents and may be used as such in the adhesives of the present invention. Typically, the amount of MQ resin required to achieve the desired levels of release and release force will depend on the total amount of high and low molecular weight polydiorganosiloxane. The amounts of each component of the adhesive of the present invention are preferably selected to provide the desired levels of release and release force described above. If the total weight (ie, parts by weight) of the MQ resin plus the polydiorganosiloxane (both high and low molecular weight) equals 100 parts, preferably at least about 50 parts by weight of MQ
The resin and up to about 70 parts by weight of MQ resin are used to achieve the desired level of release force.

Suitable organohydrogenpolysiloxanes having an average of at least two silicon-bonded hydrogen atoms in each molecule and containing no aliphatic unsaturation are Dow Corning, Midland, Michigan, and Waterford, NY, Ge
Commercially available from sources such as internal Electric Silicones. An example is disclosed in U.S. Patent No. 5,082,706 (Tangney).

Such silicone adhesives are prepared by addition cure chemistry and typically include platinum or other Group VIIIB (ie, Groups 8, 9, and 10) catalysts,
It typically involves the use of a hydrosilylation catalyst, which results in curing of the silicone adhesive. The reported benefits of addition-cured silicone adhesives include lower viscosity, higher solids, stable viscosity over time, and lower temperature curing compared to silicone adhesives prepared through condensation chemistry. Can be The method of preparation is disclosed in US Pat. No. 5,082,706 (Tangney).

The adhesive composition may include additives for controlling desired properties. For example, a pigment may be added as a colorant, a conductive compound may be added to make the adhesive surface conductive or antistatic, an antioxidant and a bacteriostatic agent may be added, and a light absorbing agent may be added. May block certain wavelengths from passing through the product, or an inhibitor may be added to extend the adhesive pot life to avoid premature gelling of the adhesive coating solution. . Examples of such additives are commercially available from various sources and are also disclosed in U.S. Pat. No. 5,082,706 (Tangney) in desired amounts.

The adhesive composition preferably has a weight of about 0.2 g / 154.2 cm ² to about 2.4 g / 1.
An adhesive / release liner laminate can be produced at a coverage of 54.2 cm ² by application to a suitable release liner in a wide variety of ways, including solution coating, solution spraying, and the like. Typically, it is a refractory group such as polyethylene terephthalate coated with a fluorosilicone release material, such as those disclosed in US Pat. No. 5,082,706 and commercially available from Rexam Release of Bedford Park, Illinois. Applied to the material to form an adhesive / release liner laminate.
The adhesive transfer tape is then laminated to the desired substrate, such as biaxially oriented polyethylene or high density polyethylene, forming an adhesive tape, especially a cover tape for the analytical container. Under the conditions described herein, a release liner that removes Dow Corning 7657 silicone adhesive with a release force of less than about 10 N / dm is desirable for evaluating the release force of the adhesive of the present invention.

Conventional cover tapes for microtiter plates include an adhesive layer and a backing material such as aluminum (Al) foil or polyethylene terephthalate (PET). Aluminum foil backing is less desirable because it is not transparent.
PET tape backing has high mechanical strength and resists all punctures except the tightest and sharpest needles. For example, plastic pipette tips require a strong force to break very thin (approximately 1 mil or 25 μm) PET backing.

A backing material suitable for use in the cover tape of the present invention allows puncturing, for example, with a needle or a plastic sampling pipette tip. Such a puncture site may or may not reclose (ie, reseal). Alternatively, a suitable backing material that resists puncturing can be used. Preferably, the backing is punctured without tearing. The backing can be transparent, translucent, or opaque. Preferably, the backing is transparent. Transparency facilitates chemical analysis performed with any of several photometric methods, including, for example, ultraviolet, visible, and fluorescence analysis.

The backing material can include a wide range of substrate materials, such as polyethylene, polyethylene terephthalate (PET), biaxially oriented polypropylene (BOPP),
And polymer films such as metallocene polymerized poly (α-olefin) copolymers. These backings, as described above for the adhesive, are generally resistant to solvents commonly used in biological analysis applications. If they are punctured, the puncture site will not reclose, but they may or may not be able to resist the puncture. A backing capable of reclosing the puncture site is also possible.

As the analysis container to which the cover tape can be applied, a wide variety of products can be mentioned. Preferably, the analysis vessel includes at least one surface having one or more reservoirs therein. For example, suitable assay vessels to which the cover tape of the present invention can be applied include microtiter plates, which are plastic plates that typically contain many aligned small flat bottom wells. Another example is a tape comprising a gel-coated substrate having a plurality of discrete adjacent tracks thereon, as disclosed in U.S. Patent No. 3,551,295 (Dyer).

Other analytical vessels include microfluidic devices that include a substrate and one or more channels therein. Such a structure, including a structure and at least one microscale channel disposed therein, is disclosed in U.S. Pat. No. 5,842,787 (
Kopf-Sill et al.). Yet another such structure recessed in a planar substrate and having grooves defining a microfluidic channel system is disclosed in U.S. Patent No. 5,443,890 (Ohman). Yet another such structure, including a substrate having microstructures formed therein, is disclosed in US Pat. No. 5,804,804.
, 022 (Kaltenbach et al.).

Another type of analytical vessel is a substantially continuous, formed at a predetermined, preferably evenly spaced along its length, having a wall portion defining a series of identical reservoirs. A polymer strip, the reservoir of which can have a variety of shapes. For example, the reservoir may include a rectangular or generally "I" or "T" shape in the strip plane, as desired, and may have a flat or round bottom. Such containers are described, for example, in US Pat. No. 4,883,642 (Biscont).
e). Another disclosed in US Pat. No. 5,729,963 (Bird) is designed for transporting electrical components, but can be modified for use as an analysis vessel.

These analytical vessels are filled with carbon black or TiO ₂ , transparent, translucent,
Alternatively, it can be formed from various materials including polyethylene, polystyrene, polypropylene, and polycarbonate, which may be opaque.

EXAMPLES The following examples further illustrate the objects and advantages of this invention, but the particular materials and amounts, as well as other conditions and details, set forth in these examples unduly limit the invention. Shall not.

Test Method Peel Force Test: A 1 inch (2.54 cm) by 6 inch (15.24 cm) strip of each test adhesive tape sample was placed on a 20 mil (0.05 cm) thick polypropylene plate. The tape was then applied to the plate assembly using a 5 lb (2.27 kg) roller to ensure uniform contact. Subsequently, ASTM was performed using an Imas slip / peel tester model SP-102B-3M90 (Instrumentors Inc. of Strongsville, OH).
Plate speed 12 in / min (30 in accordance with D3330-D3330M-96)
. (5 cm / min), the 180 ° peel force between the silicone adhesive and the polypropylene plate was measured. The average peel force per inch of plate movement was recorded on the tester. Repeat the test three times and average the value in Newtons per decimeter (N / dm)
Reported in.

Peel Strength Test: Tape Backing, Silicone Adhesive Layer, and Fluorosilicone Coated Release Liner (Rexam Release, Bedford Park, Ill.)
A 1 inch (2.54 cm) wide by 6 inch (15.24 cm) long tape laminate of CLPET-6J / 000 (available from SE Corporation) was cleaned with an Imas tester (Model SP-102B-3M90). The glass base plate was adhered with SCOTCH tape # 411 (3M Company, St. Paul, Minn.). The 180 ° peel force between the release liner and the silicone adhesive was measured at a rate of 30.5 cm / min by pulling the backing / adhesive laminate from the release liner according to ASTM D3330-D3330M-9. The average peel force per inch of plate movement was recorded on the tester. The experiment was repeated three times and the average was reported in N / dm.

Cross-contamination test: In a polystyrene 96-well microplate (available from Nalge International Corp., Naperville, Ill.), Approximately 50 μl of red colorant solution (MERTHIOLATE supplied by Eli Lilly, diluted approximately 1:50 with water) ), The wells were alternately filled, and the well openings of the microplate were covered with sample adhesive cover tape. The covered plate was subsequently turned over and rocked several times. Next, the wells in the plate were visually inspected to determine whether the indicator solution had moved to adjacent wells.

Solvent resistance test: 6 each having dimensions of 0.6 cm diameter × 0.6 cm depth
The sample adhesive tape was adhered to an aluminum plate having individual wells. Before applying the cover tape, each well was filled with DMSO (50 μl) and the wells covered with the tape were left for 24 hours. Subsequently, the tape was visually inspected for evidence of swelling or dissolution.

Extract Test: Each adhesive cover tape of a sample (4 cm × 5 cm) was immersed in 5 ml of water or dimethyl sulfoxide (DMSO) for 24 hours. The sample adhesive tape was also exposed to gas phase contact with a solvent for 7 days in wells of an aluminum plate coated with the sample adhesive tape described above. Model ZB-5 column (length 30)
m, inner diameter 0.25 mm, film 0.1 μm, Phenom, CA
4x Atas Optic (available from Enex Torrance)
2 injector (available from Atas, Cambridge, Cambridgeshire, UK),
And Thermoquest Corporation of San Jose, California
Finnigan "Magnum" GC equipped with a Finnegan scanning electron impact detector (electron impact scanning range 31 Dalton to 550 Dalton) available from ION
/ Ion Trap Mass Spectrometer (Thermoque, San Jose, CA)
The extract was examined by gas chromatography / mass spectroscopy (GC / MS) using St. Corporation. The Atas injector was operated in a cold split, multiple capillary liner mode at a helium carrier gas flow rate of about 1 ml / min. The injection temperature is programmed to 350 ° C. at 30 ° C./sec, starting at 50 ° C. and progressively increasing to a final temperature of 320 ° C. at 20 ° C./min and holding for 2.5 minutes at the end of the run. The temperature was programmed and the transfer line temperature was set at 300 ° C. Helium carrier gas pressure was initially programmed from 10 pounds per square inch (psi) to 20 psi after 16 minutes.

Probe Puncture Residual Adhesive Test: The described composition sample tape was applied to a clear polystyrene 96-well untreated microplate (Corni, Corning, NY).
ng Inc. No. available from 3367). Place each cover tape on a 22 gauge needle or 10 μl plastic tip (Eppendor, Germany)
f Corp. Puncture at different locations five consecutive times. Following the puncture of each tape, the needle barrel and plastic tip were visually inspected (10x magnification) for evidence of adhesive residue attached to these puncture devices.

Sample evaporation rate test: PCR (Polymerase Chain Reaction) 96-well polypropylene Microamp optical plate, model N-8010560 (Perkin Elmer BioSystems Co., Norwalk, CT)
. (Available from Co., Ltd.) was filled with 50 μl of solvent. The test sample of the adhesive cover tape was then adhered to a Microamp optical plate to cover the well opening. Changes in weight loss due to water evaporation as a function of elapsed time at room temperature (approximately 24 ° C.) over 24 hours were monitored gravimetrically to detect changes.

Examples 1-25 Materials Using xylene as a diluent, 56.5 parts silicone solids (molecular weight approx.
44% by weight of 000 vinyldimethylsiloxane-terminated polydimethylsiloxane
And a non-reactive MQ tackifying resin (56% by weight).
g7657 (Dow Corning Corp., Midland, Michigan)
silicone adhesive) (available from Nation). An additional amount of the same non-reactive MQ tackifying resin is added to the Dow Corning 7657 adhesive by the manufacturer,
An adhesive solution 76 containing 58, 60, 62 and 64% by weight of MQ, respectively.
57-2, 7657-4, 7657-6, and 7657-8 were provided. To facilitate coating, toluene (Woru, St. Paul, Minn.)
m Chemical Company) (available from Chemical Company) was added to each formulation to provide an adhesive with 40% solids by weight.

Dow Cornin containing dimethylvinylated and trimethylated silica
g SYL-OFF 7615 Release Modifier (designated 7615) (Dow Corning Corporation, Midland, Mich.) Approximately 40% by weight, 57% by weight dimethylvinyl terminated dimethylsiloxane with a degree of polymerization of 25,
Tetra (trimethylsiloxy) silane 1% by weight, Dow Corning proprietary ester 1% by weight, and a platinum containing catalyst.

Dow Cor containing dimethylsiloxane methylhydrogensiloxane copolymer
ning SYL-OFF 7678 crosslinker (designated 7678).

Dow Corning SYL containing dimethylvinyl-terminated polydimethylsiloxane, tetramethyldivinyldisiloxane, and platinum siloxane complex
OFF 4000 catalyst (referred to as 4000).

Formulation Adhesive composition A: 40% solids in toluene / xylene Dow Cornin
g7657 silicone 250 parts adhesive and 1 part SYL-OFF4000 catalyst. Adhesive composition B: 40% solids in toluene / xylene Dow Cornin
g7657-2 250 parts silicone based adhesive, and SYL-OFF400
0 parts of catalyst. Adhesive composition C: 40% solids in toluene / xylene Dow Cornin
g7657-4 250 parts of silicone based adhesive and SYL-OFF40
1 part of 00 catalyst. Adhesive composition D: Dow Cornin at 40% solids in toluene / xylene
g7657-6 250 parts of silicone-based adhesive, 1 part of SYL-OFF4000 catalyst. Adhesive composition E: Dow Corni at 40% solids in toluene / xylene
ng7657-8 250 parts of silicone-based adhesive and SYL-OFF4
000 catalyst 1 part. Modifier 7615: 93 parts of SYL-OFF7615 release modifier and SYL-O
7 parts of FF7678 crosslinking agent.

The silicone adhesives were prepared according to the formulations listed above in the ratios disclosed in Tables 1-5. Adhesive compositions AE were prepared by combining the above listed components together and mixing on a roller at room temperature for 2-4 hours. Modifier 7615 was added to adhesive compositions AE and mixed on a roller at room temperature for an additional 2-4 hours to obtain a homogeneous adhesive solution for coating.

The resulting adhesive solution was applied to a release liner (Rexam Release, Bedford Park, Ill.) Using a 6-7 mil orifice knife coater.
Corp .. CLPET-6J / 000 transfer liner) and dried and cured by passing through an oven with three zones at a speed of 3 feet / minute (0.914 m / minute). The oven zone temperature and residence time were 71 ° C. for 3 minutes each,
82 ° C. for 3 minutes and 82 ° C. for 6 minutes. Use a balance to apply 15
It was confirmed that the weight was about 0.768 to 0.896 g per 4.8 squares.

Next, the adhesive / release liner laminate and the embossed tape backing material were passed through a nip roll, and the silicone adhesive / release liner laminate was subjected to a 0.01 cm thick corona-treated ethylene / propylene copolymer (PP-PE). ) Film (BPI Code No. 26379-3 from Bloomer Plastics Inc. of Bloomer, WI) was laminated to an embossed tape backing.

A peel force test and a peel force test were measured for each of the prepared samples.
5 reported. The results suggested that the addition of 0-20 parts of the silicone modifier to the silicone adhesive had a slight effect on the peel strength of the silicone tape. Surprisingly, the results show that the addition of the silicone modifier plays a role in reducing the peel strength without adversely affecting the peel adhesion.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5]

Examples 26-47 and Comparative Examples C1-C5 Materials Dow Corning 7657 silicone adhesive diluted to 40 wt% solids with toluene. Vinyl liquid A: a vinyldimethylsiloxane-terminated polydimethylsiloxane liquid having a degree of polymerization of 24. Vinyl liquid B: a vinyldimethylsiloxane-terminated polydimethylsiloxane liquid having a degree of polymerization of 67. Vinyl liquid C: a vinyldimethylsiloxane-terminated polydimethylsiloxane liquid having a degree of polymerization of 101. Vinyl liquid D: a vinyldimethylsiloxane-terminated polydimethylsiloxane liquid having a degree of polymerization of 167. Vinyl liquid E: a vinyldimethylsiloxane-terminated polydimethylsiloxane liquid having a degree of polymerization of 245. Vinyl liquid F: a vinyldimethylsiloxane-terminated polydimethylsiloxane liquid having a polymerization degree of 459. MQ resin solution: 63.4% non-reactive MQ resin in xylene (Dow Cor)
ning7657 silicone adhesive), Dow Corning
Provided by 2EHHM: 2-ethylhexyl hydrogen maleate was prepared by reacting 1 mole of maleic anhydride with 1 mole of 2-ethyl-1-hexanol.

Formulations Masterbatches of low molecular weight vinyl substituted polydiorganosiloxanes ("vinyl liquors" having different degrees of polymerization) were prepared according to the following formulation.

[0073]

[Table 6]

In each of the following examples, an appropriate amount of each master batch shown in Tables 6-11 was added to 50 g of 40% solids Dow Corning 7657 and 0.2 g of SYL-OF.
It was mixed with F4000. Before coating using a tumbling roller for 2-4 hours,
Ensure uniform mixing.

The resulting adhesive solution was applied to a release liner (Red, Bedford Park, Illinois).
Examples 1 to 4 except that oven zones 1, 2, and 3 were set to temperatures of 125 ° C., 149 ° C., and 149 ° C., respectively, applied on a CLPET-6J / 000 transition liner from xam Release. Coating and drying were carried out in the same manner as in No. 25. The adhesive / release liner laminate was then applied to 3M, St. Paul, Minn.
31 μm thickness available from the Company under the trade name SCOTCHPRO
(1.2 mils) was laminated to a BOPP (biaxially oriented polypropylene film) tape backing. The BOPP tape backing was corona treated to improve the bonding of the silicone adhesive. The transfer tape and backing were passed through a nip roll to build the adhesive and liner and backing laminate.

The peel force and the peel force of the tape were measured using the respective tests described above and reported in Tables 6-11. The peel force of Example C1, which corresponds to the formulation of Example 1, was dramatically increased. This suggests that the fluorosilicone release liner used for Tables 6-11 is less effective than that of Tables 1-5 (due to lot-to-lot variation). Nevertheless, the results of Examples 1 to 25 and 26 to 47 show that the addition of low molecular weight silicone vinyl liquid (with or without reactive MQ resin) in the silicone adhesive formulation shows that the peel adhesion It confirms that it has a significant effect on reducing the release force of the silicone adhesive from the release liner without adversely affecting the release. The data also suggests that a wide range of low molecular weight vinyl-functional silicone fluids can be added into silicone-based adhesives with little effect on the release force of the silicone tape.

[0077]

[Table 7]

[0078]

[Table 8]

[0079]

[Table 9]

[0080]

[Table 10]

[0081]

[Table 11]

[0082]

[Table 12]

Examples 48-49 and Comparative Examples C6-C11 Release Liners (Rexam Releases, Bedford Park, Illinois)
e The CLPET-6J / 000 transfer liner from Corporation) was laminated to the following backing material.

Example 48 used embossed high density polyethylene referred to as PE (product number B100NA from Bloomer Plastics, Bloomer, WI). The thickness of the embossed film was 101.6 μm (4 mil).

Example 49 is referred to as BOPP and is a 3M Comp of St. Paul, Minn.
any thickness 30.5 μm (1) available under the SCOTCHPRO trade name from Any.
. 2 mil) was used.

[0086] Polystyrene 96-well microplates (Naperville, IL)
lge International Corp.), approximately 50 μl of the red colorant solution (MERTHIO supplied by Eli Lilly)
The wells were alternately filled with LATE (diluted approximately 1:50 with water) and the well openings of the microplate were covered with the sample adhesive cover tape of Examples 48 and 49. The covered plate was subsequently turned over and rocked several times. Next, the wells in the plate were visually inspected to determine whether the indicator solution had moved to adjacent wells.

The tape samples of Examples 48 and 49 were affixed onto 96-well polypropylene microplates (Catalog No. 3364, available from Corning Inc., Corning, NY) and DMSO was placed in the microwells for 24 hours at ambient conditions. I left it. There was no noticeable change in the adhesion of the inventive cover tape to the polypropylene plate. However, nitrile rubber adhesive tape labels (Minnesota Mining and Manufac, St. Paul, Minn.)
turning Co. Comparative Example C consisting of product number SJ3101) available from
6, and PET backing adhesive tape (PGC, Gaithersburg, MD)
Comparative Example C7 (THINSEAL tape available from Scientifics) showed complete loss of adhesion when exposed to the same test conditions, as shown in Table 12, respectively.

These four identical cover tapes were adhered to a clear polystyrene 96-well untreated microplate (No. 3367 available from Corning Inc., Corning, NY). Each cover tape was punctured five times in succession with a 22 gauge needle at different locations. Following the puncture of each tape, the needle barrel and plastic tip were visually inspected (10x magnification) for evidence of adhesive residue attached to these puncture devices. Table 12 shows the results.

[0089]

[Table 13]

Table 13 shows the typical biological analysis laboratories obtained from extract tests using the GC / MS conditions listed above for preparing samples to be coated in multi-well aluminum plates. We report the extraction data with some common solvents used in the process. Tape samples were placed in DMSO, water, and an 80/20 acetonitrile / water mixture for 24 hours. All extracts were analyzed by GC / MS. The results showed that no material was extracted from these tapes.

Comparative Example 8 was obtained from Corning Corp., New York. Corning cover tape (product no. 3095) commercially available from KK. Comparative Example 9
Is available from Zymark Corp., Hopkinton, Mass. The product was a cover tape having a product number of 62367. Comparative Example 10 was from Corning Costar Corp., Acton, Mass. Co available from
Star product number 6569 cover tape. Comparative Example 11 was an Ultra plate cover tape available from Sagian Corporation of Indianapolis, Indiana. Each of these cover tape samples was used as it was. The results demonstrate that a significant value of the present invention is the ability of the cover tapes of the present invention to resist solvents commonly used in biological analysis applications.

[0092]

[Table 14]

Evaporation Rates of Example 42 and Comparative Example 12 Table 14 compares the water evaporation rates within 24 hours for cover tapes affixed to Perkin Elmer PCR 96-well plates. Tape is 27N /
The silicone cover tape of Example 42 having a peel strength of about dm and the CYCLE SE of Comparative Example 12 having a peel strength of less than 5 N / dm.
AL Cover Tape (Robbins Scie, Sunnyvale, CA)
ntic Corp. ). The data showed that the silicone tape of the present invention provided a better seal to plate wells as compared to a commercially available cover tape with low peel adhesion.

[0094]

[Table 15]

Evaporation Rate of Example 50 and Comparative Examples 13-15 Example 50 shows three layers for the adhesive of Example 42 and the adhesive tape backing (
A / B / A) Coextruded film with outer layer A (7 μm thickness) FINA polypropylene # 3825 (FINA Oil & Chemi, Dallas, Texas)
cal Co. B available from KRATON G1657 (available from Shell Chemical, Houston, TX) (thickness = 63).
μm). Films were prepared on a co-extrusion line using a Cloeren (Oregon, TX) ABBBC feed block. Layer B (elastic core) was split into three layers in the feed block and recombined to sandwich between the two skin layers to form a three-layer coextruded film. Layer A (skin 1) was cast on a rubber nip roll. Layer C (skin 2) was cast on a patterned steel chill roll. Extruder A (Skin 1) is from David Standard Cor
2.5 inch single screw (24: 1 L / D) manufactured by N.Poration (Paucatac, CT). Extruder B (elastic core)
Extruders Inc. Extruder C (skin 2) is a 2.5 inch single screw (32: 1) manufactured by David Standard
1.5 inch single screw (24: 1 L / D).

Comparative Examples 13 and 14 were commercially available adhesive tapes. Aluminum adhesive tape (Comparative Example 13, Marsh Biomedica, Rochester, NY)
l Products, Inc. And adhesive tape (Comparative Example 14, THINSEAL trade name from MDPGC Scientifics, Gaithersburg, MD) was used for comparison. Comparative Example 15 was an open well (no cover tape).

After removing the release liners from the tapes of Example 50 and Comparative Examples 13 and 14, they were filled with 50-ml water of each well of a 96-well polypropylene Microamp optical plate model N-8010560 (Norwalk, CT). (Available from Perkin Elmer Bio Systems Co., Inc.) was used as a cover tape to seal.

In the first experiment, the adhesive was brought into contact with the openings of the microwells,
The microplate covered with the adhesive cover tape was inverted. The tape of Example 50 was then punctured several times using an 18 gauge stainless steel needle of a hypodermic syringe,
Removal of water from selected microwells was facilitated. After withdrawing the needle and inverting the microplate, there was no visible evidence of leakage from any of the microwells covered with the tape of Example 50. It should also be noted that after the penetration test was completed, there was no evidence of adhesive residue on the probe surface used to puncture the cover tape of Example 50.

In the second experiment, the cover tape of each of Example 50 and Comparative Examples 13 and 14 was punctured with a 22-gauge needle under room conditions. Table 15 shows 96-well polypropylene Microamp optical plate model N-80105 filled with a representative solvent.
60 (Perkin Elmer Bio Sy, Norwalk, CT)
stems Co. (Available from Co., Ltd.) on the surface of the pierced cover tape of this second experiment. The solvents covered by the tape were acetonitrile / water (weight ratio 84:16), water, and DMSO. Compared to Comparative Examples 13 and 14, Example 50 had minimal loss due to evaporation and no leakage was detected after shaking the plate vigorously. The negative value of Example 50 for DMSO appeared to be due to moisture adsorption by DMSO at room conditions. Comparative Example 1
5 shows the evaporation rate of the solvent without the cover tape.

[0100]

[Table 16]

Cover Tape Peel Force from Nitrile Rubber Using the peel force test described above, except that a portion of the nitrile rubber glove was adhered to a polypropylene plate with SCOTCH tape # 411 (3M Company, St. Paul, Minn.). , Nitrile rubber surface (Type: N-DEX60
005PFM Powder Free, Best Manufac, Menio, GA
turning Co. ) Was measured. Examples 11 to 1
Table 16 shows the data of the cover tape for Comparative Example 5 and Comparative Example 14. The silicone tape of the present invention has very low peel adhesion to commonly used rubber gloves. In addition, silicone tapes have very low tackiness when touched with fingers or rubber gloves.

[0102]

[Table 17]

The complete publications of the patents, patent documents, and publications cited herein are individually incorporated by reference in their entirety. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. The invention is not unduly limited by the illustrative embodiments and examples described herein, such examples and embodiments being presented for illustration only, and the scope of the invention will now be described hereinafter. It shall be limited only by the claims.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G01N 35/02 G01N 35/02 A (81) Designated country EP (AT, BE, CH, CY, DE, DK) , ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR) , NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU) , TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV , MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Melancon, Cartsy. United States, Minnesota 55110, White Bear Lake, North One Handed Twenty Fifth Street 6480 (72) Inventors Schulz, Anita El. United States, Minnesota 55110-1420, Delwood, Glen H. Load 61 F term (reference) 2G058 AA09 CA01 CA02 CC01 CC02 GA01 4J004 AA11 AA17 AA18 AB01 CA04 CA06 CC02 DB03 FA06 FA09 FA10 GA01 4J040 EK041 EK051 EK091 HD43 JA09 JB09 KA14 LA06 MA10 NA06 PA23

Claims (34)

[Claims] (1) A general formula: R ¹ R ₂ SiO (R ₂ SiO) _n SiR ₂ R ¹ wherein each R is independently a monovalent hydrocarbon group, and each R ¹ is independently An alkenyl group, n is an integer) and a polydiorganosiloxane having a number average molecular weight of at least 20,000; (b) a general formula: R ¹ R ₂ SiO (R ₂ SiO) _m (R ¹ RSiO) _n SiR ₂ R ¹ (wherein each R and R ¹ are independently a monovalent hydrocarbon group, at least two R ¹ groups are alkenyl groups, m and n are integers, and the total 250 to about 1
It provides an alkenyl equivalent of 000. And (c) (R ² ) ₃ SiO _1/2 units, wherein each R ² is independently a group of alkyl, alkenyl, or hydroxyl groups. And at least 95 mol% of all R ² groups
Is a methyl group. ) And an SiO ₂ unit in a molar ratio in the range of 0.6: 1 to 1: 1; and (d) 1 to 40 alkenyl groups in the components (a) to (c). (E) an aliphatic unsaturation-free organohydrogenpolysiloxane having an average of at least two silicon-bonded hydrogen atoms in each molecule in an amount sufficient to provide the silicon-bonded hydrogen atoms of 0.1 parts by weight per 1 million parts by weight of the total of the components (a) to (d)
An amount of a Group VIIIB-containing catalyst sufficient to provide １，1,000 parts by weight of a Group VIIIB metal. 2. The adhesive of claim 1, wherein the organopolysiloxane MQ resin comprises both non-functional and functional MQ resins. 3. The adhesive according to claim 2, wherein the functional MQ resin contains alkenyl groups. 4. A coating weight of 0.8 g / 15 on a fluorosilicone-coated polyethylene terephthalate release liner and a propylene / ethylene copolymer backing material.
When placed at 4.8 cm ² to form a laminate and adhered to a glass plate, 180 ° less than about 20 N / dm when measured at room temperature at 30.5 cm / min.
The adhesive of claim 1, which exhibits a peel force. 5. The adhesive of claim 4, which exhibits a peel force of about 15 N / dm or less. 6. The adhesive of claim 5, which exhibits a peel force of less than about 10 N / dm. 7. The adhesive of claim 6, which exhibits a peel force of about 5 N / dm or less. 8. 0.8 g / 154 on a propylene / ethylene copolymer backing material.
. The adhesive of claim 1 wherein the adhesive is disposed at a coat weight of 8 cm ² and exhibits a 180 ° peel force of at least about 5 N / dm when bonded to a polypropylene plate when measured at room temperature at 30.5 cm / min. . 9. The adhesive according to claim 1, which is a pressure-sensitive adhesive. 10. An adhesive product, wherein the silicone-based adhesive of claim 1 comprises a substrate disposed on at least one major surface. 11. The adhesive product according to claim 10, wherein the organopolysiloxane MQ resin comprises both non-functional and functional MQ resins. 12. The adhesive product according to claim 10, further comprising a release liner disposed on the adhesive. 13. An adhesive having a fluorosilicone-coated polyethylene terephthalate release liner and a propylene / ethylene copolymer backing.
8 g / 154.8 cm ² laid down to form a laminate and adhered to a glass plate, when measured at room temperature at 30.5 cm / min, about 20 N /
The adhesive product according to claim 10, which exhibits a 180 ° peel force of dm or less. 14. The adhesive product of claim 13, wherein the adhesive exhibits a peel force of about 5 N / dm or less. 15. The method of claim 1 wherein the adhesive is 0.8 on the propylene / ethylene copolymer backing.
g / 154.8 cm ² and when adhered to a polypropylene plate, at least about 5 N / d when measured at 30.5 cm / min at room temperature.
An adhesive product according to claim 10 exhibiting a 180 ° peel force of m. 16. The adhesive product of claim 10, wherein the backing comprises a pierceable material. 17. The adhesive product according to claim 10, wherein the adhesive is a pressure-sensitive adhesive. 18. An analytical container comprising a surface and a cover tape adhered to the surface, wherein the cover tape is disposed on at least one major surface of the backing material and contacts the container surface. Item 7. An analysis container comprising the adhesive according to item 1. 19. The analysis container according to claim 18, further comprising a well or channel in the form of one or more reservoirs. 20. The analysis container according to claim 18, wherein the analysis container comprises a substantially continuous tape. 21. The analysis container according to claim 18, wherein the adhesive is a pressure-sensitive adhesive. 22. An adhesive comprising 0.8 g on a fluorosilicone-coated polyethylene terephthalate release liner and a propylene / ethylene copolymer backing material.
/154.8 cm ² , placed in a coating amount to form a laminate and, when adhered to a glass plate, exhibit a 180 ° peel force of about 20 N / dm or less when measured at room temperature at 30.5 cm / min. Item 19. The analysis container according to Item 18. 23. The analytical container of claim 22, wherein the adhesive exhibits a peel force of about 5 N / dm or less. 24. An adhesive having a propylene / ethylene copolymer backing of 0.8
20. The method according to claim 18, wherein when disposed at a coverage of g / 154.8 cm ² and adhered to a polypropylene plate, it exhibits a 180 ° peel force of at least about 5 N / dm when measured at room temperature at 30.5 cm / min. The analysis container according to the above. 25. The analytical container of claim 18, further comprising one or more reservoirs having a liquid therein during use. 26. The liquid comprising dimethyl sulfoxide, water, acetonitrile / water,
The analysis container according to claim 25, comprising methanol, ethanol, or a mixture thereof. 27. The analysis container according to claim 18, comprising a microtiter plate. 28. The analytical container of claim 18, comprising a microfluidic device comprising a substrate and one or more channels therein. 29. The analytical vessel of claim 18, comprising a substantially continuous polymer strip comprising a plurality of reservoirs at predetermined intervals along a length. 30. The analysis container according to claim 29, wherein the reservoirs are evenly spaced. 31. An analytical container comprising a surface comprising polypropylene, polystyrene, or a combination thereof, and a cover tape adhered to the surface,
The cover tape includes a backing material and an adhesive disposed on at least one major surface of the backing material and in contact with a container surface, the adhesive comprising: (a) a general formula: R ¹ R ₂ SiO (R ₂ SiO) (b) a polydiorganosiloxane having _n SiR ₂ R ¹ , wherein each R is independently a monovalent hydrocarbon group, each R ¹ is independently an alkenyl group, and n is an integer. (R ² ) ₃ SiO _1/2 units (each R ² is independently an alkyl group, an alkenyl group,
Or at least 95 mol% of all R ² groups are methyl groups. ) And SiO ₂ units from 0.6: 1 to 1: Organopolysiloxane MQ resin containing a molar ratio of 1 range, (c) if present, per alkenyl group in component (a) ~ (c) 1-4
An aliphatic unsaturation-free organohydrogenpolysiloxane having an average of at least two silicon-bonded hydrogen atoms in each molecule in an amount sufficient to provide zero silicon-bonded hydrogen atoms; and d) 0.1 parts by weight of 1,000,000 parts by weight of the total amount of the components (a) to (c)
An analytical vessel prepared from components comprising: -a Group VIIIB-containing catalyst in an amount sufficient to provide ~ 1,000 parts by weight of a Group VIIIB metal. 32. An analytical container comprising a surface and a cover tape adhered to the surface, wherein the cover tape is disposed on at least one major surface of the backing material and the adhesive contacts the container surface. And (e) a general formula: R ¹ R ₂ SiO (R ₂ SiO) _n SiR ₂ R ¹ (wherein each R is independently a monovalent hydrocarbon group, and each R ¹ Is independently an alkenyl group, and n is an integer.) (F) (R ² ) ₃ SiO _1/2 units, wherein each R ² is an alkyl group, an alkenyl group, or a hydroxyl group. At least 95 mol% of all R ² groups independently selected from the group of groups
Is a methyl group. ) And SiO ₂ units from 0.6: 1 to 1: Organopolysiloxane MQ resin containing a molar ratio of 1 range, (g) if present, alkenyl in component (a) and component (b) Aliphatic unsaturation-free organohydrogenpolysiloxane having an average of at least two silicon-bonded hydrogen atoms in each molecule in an amount sufficient to provide from 1 to 40 silicon-bonded hydrogen atoms per group Siloxane and (h) 0.1 parts by weight of 1,000,000 parts by weight of the total amount of components (a) to (c).
Wherein the adhesive is prepared from a component comprising a sufficient amount of a Group VIIIB-containing catalyst to provide ~ 1,000 parts by weight of a Group VIIIB metal, wherein the adhesive comprises a fluorosilicone-coated polyethylene terephthalate release liner;
And placed on a propylene / ethylene copolymer backing material at a coverage of 0.8 g / 154.8 cm ² to form a laminate and adhered to a glass plate when measured at 30.5 cm / min at room temperature. An analysis container exhibiting a 180 ° peel force of about 20 N / dm or less. 33. (a) General formula: R ¹ R ₂ SiO (R ₂ SiO) _n SiR ₂ R ¹ (wherein each R is independently a monovalent hydrocarbon group, and each R ¹ is independently An alkenyl group, n is an integer.) And a polydiorganosiloxane having a number average molecular weight of at least 20,000; (b) a general formula: R ¹ R ₂ SiO (R ₂ SiO) _m (R ¹ R ₂ SiO _N SiR ₂ R ¹ (wherein each R and R ¹ are independently a monovalent hydrocarbon group, at least two R ¹ groups are alkenyl groups, m and n are integers, and Is about 250 to about 1
It provides an alkenyl equivalent of 000. And (c) (R ² ) ₃ SiO _1/2 units, wherein each R ² is independently a group of alkyl, alkenyl, or hydroxyl groups. And at least 95 mol% of all R ² groups
Is a methyl group. ) And an SiO ₂ unit in a molar ratio in the range of 0.6: 1 to 1: 1; and (d) 1 to 40 alkenyl groups in the components (a) to (c). (E) an aliphatic unsaturation-free organohydrogenpolysiloxane having an average of at least two silicon-bonded hydrogen atoms in each molecule in an amount sufficient to provide the silicon-bonded hydrogen atoms of 0.1 parts by weight per 1 million parts by weight of the total of the components (a) to (d)
Preparing a composition comprising a sufficient amount of a Group VIIIB-containing catalyst to provide 〜1,000 parts by weight of a Group VIIIB metal; and heat curing the composition. Method. 34. A method for sealing an analytical container comprising the step of applying a cover tape comprising a backing material and an adhesive according to claim 1 disposed on at least one major surface thereof.