Cyanoacrylate Composition

Abstract

FIELD OF THE INVENTION The present invention relates to curable cyanoacrylate compositions suitable for use as adhesive compositions, for example in the form of tapes.

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention relates to curable cyanoacrylate compositions suitable for use as adhesive compositions, for example in tape form. [Background technology]

[0002] Cyanoacrylate monomers that are solid at room temperature, such as phenylethyl cyanoacrylate, ethylhexyl cyanoacrylate, and hexadecyl cyanoacrylate, are known. These room-temperature solid cyanoacrylate monomers can be used to prepare stick and tape-form cyanoacrylate products. However, compositions based on these monomers perform poorly across a range of metrics compared to compositions containing conventional room-temperature liquid cyanoacrylate monomers. Furthermore, solid cyanoacrylate monomers are typically non-standard specialty chemicals that are expensive and difficult to synthesize.

[0003] The cyanoacrylate tapes developed by Henkel to date are based on monomers that are solid at room temperature, such as phenylethyl cyanoacrylate. However, using solid cyanoacrylate monomers to produce adhesive tapes would preclude their use as "instant-stick" tapes, eliminating the main advantage of using cyanoacrylates as instant adhesives.

[0004] Liquid cyanoacrylate monomers diffuse better through the bulk and cure faster at room temperature than solid cyanoacrylate monomers.

[0005] However, tapes based on standard liquid cyanoacrylate monomers are difficult to achieve due to the inherent reactivity of cyanoacrylate monomers with film formers as well as the need for materials with sufficient structural integrity to achieve adequate film formation.

[0006] A rare example is that described in U.S. Patent Application No. 2015 / 0107761, which discloses a tape comprising a curable film on a release substrate and / or carrier substrate, the curable film comprising at least one cyanoacrylate monomer and at least one film-forming (co)polymer.

[0007] It would be advantageous to develop an adhesive tape that achieves instant adhesion without the need for heat under pressure. Summary of the Invention [Means for solving the problem]

[0008] In one aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis. a cyanoacrylate component, and solid thermoplastic polyether polyurethane resin, A curable composition comprising: The solid thermoplastic polyether polyurethane resin comprises a curable composition having a molecular weight Mw ranging from about 180,000 g / mol to about 260,000 g / mol, the molecular weight Mw being measured according to ASTM D5296-05.

[0009] The compositions of the present invention are non-flowable at room temperature (25°C) and are suitable for use as adhesive compositions. Desirably, the compositions of the present invention are substantially solid and can be used to provide any suitable solid form. The compositions of the present invention can be used in any suitable application, for example, in the form of a tape. The compositions of the present invention can be provided on a carrier or can be self-supporting. For example, the compositions can be coated onto a release liner, and an intermediate liner layer or a liner with a different release value can be used. The compositions can be coated using a suitable solvent, for example, cast onto a liner from a suitable solvent.

[0010] The solid thermoplastic polyether polyurethane resin may have a molecular weight Mw in the range of about 200,000 g / mol to about 240,000 g / mol, such as about 215,000 g / mol to 230,000 g / mol, for example, 220,000 g / mol to 225,000 g / mol, for example, about 223,000 g / mol, where Mw is determined according to ASTM D5296-05 (Standard Test Method for Molecular Weight Average and Molecular Weight Distribution of Polystyrene by High Performance Size Exclusion Chromatography).

[0011] The solid thermoplastic polyether polyurethane resin may have a melting point in the range of 160°C to 200°C, such as 165°C to 190°C, for example 170°C to 180°C.

[0012] Suitably, the cyanoacrylate component is a liquid curable cyanoacrylate component.

[0013] The cyanoacrylate component (i) may be selected from the group including ethyl cyanoacrylate, butyl cyanoacrylate, β-methoxy cyanoacrylate, and combinations thereof.

[0014] The solid thermoplastic polyether polyurethane resin may be present in an amount of from about 25% to about 90% by weight based on the total weight of the composition, suitably greater than 50% by weight, for example, from about 65% to about 85% by weight based on the total weight of the curable composition.

[0015] Without being bound by theory, compositions containing less than about 25 wt.% of a solid thermoplastic polyether polyurethane component may not have sufficient elastic properties to allow proper application of the composition to parts to be bonded. Compositions containing more than about 90 wt.% of a solid thermoplastic polyether polyurethane component may have poor adhesive properties. When the solid thermoplastic polyether polyurethane resin is present in an amount of about 25 wt.% to about 90 wt.%, based on the total weight of the curable composition, this can provide an acceptable balance between adhesive performance and the ability to form a coating with sufficient elastic properties to allow application of the composition to parts to be bonded.

[0016] The cyanoacrylate component (i) may be present in the curable composition in an amount of from about 10% to about 75% by weight, suitably from about 10% to 50% by weight, for example from 15% to about 35% by weight, the weight percentage being based on the total weight of the composition.

[0017] The present invention may include a stabilizer for the cyanoacrylate component.

[0018] In some embodiments, the stabilizer for the cyanoacrylate component is present in an amount of from about 10 ppm to about 200 ppm, such as from about 25 ppm to about 100 ppm.

[0019] The stabilizer may be selected from boron trifluoride (BF3) or sulfur dioxide (SO2).

[0020] The stabilizer is preferably sulfur dioxide (SO2).

[0021] The compositions of the present invention may further comprise at least one solvent, the use of which may be beneficial for formulation or dispensing purposes, for example.

[0022] However, whenever weight percentages are used, they are based on the total weight of the composition excluding solvent.

[0023] In some embodiments, the present invention comprises a solvent selected from the group including ethyl acetate, tetrahydrofuran, methyl ethyl ketone, cyclohexanone, and acetone.

[0024] The present invention preferably includes ethyl acetate as the solvent.

[0025] The compositions of the present invention may be provided in any suitable solid form, such as in tape form, filament form, or as a coating applied to a substrate.

[0026] Suitably, the compositions of the present invention are provided in tape form.

[0027] In another aspect, the present invention also relates to a tape comprising a curable composition according to the present invention and one or more release liners.

[0028] The tape of the present invention may be a transfer tape. The release liner may be used to transfer the curable composition, for example in film form, to at least one substrate.

[0029] The tape of the present invention may exhibit adhesive properties at room temperature, and the curable composition of the article may adhere to at least one surface by applying light pressure to the tape. The cyanoacrylate component of the composition functions as an instant adhesive. Therefore, the composition of the present invention should instantly adhere to any compatible substrate.

[0030] In another aspect, the present invention also provides a method for producing a pharmaceutical composition comprising: i) combining the solid thermoplastic polyether polyurethane resin component, the cyanoacrylate component, and a solvent to form a mixture; ii) applying the mixture of step (i) to a substrate, optionally by casting; iii) evaporating the solvent or actively removing the solvent, thereby forming a solid curable composition; The present invention relates to a method for preparing a curable composition, comprising:

[0031] In some embodiments of this method, the substrate is a release liner.

[0032] In some embodiments of this method, the solvent is ethyl acetate.

[0033] In some embodiments of this method, the solid thermoplastic polyether polyurethane resin is present in the curable composition in an amount greater than about 50% by weight, the weight percent being based on the total weight of the composition.

[0034] The solid thermoplastic polyether polyurethane resin may be present in an amount equal to or greater than the cyanoacrylate component.

[0035] In another aspect, the present invention also relates to the compositions of the present invention in cured form.

[0036] In yet another aspect, the present invention also relates to an assembly comprising two substrates adhered together by the composition of the present invention in cured form. DETAILED DESCRIPTION OF THE INVENTION

[0037] As noted above, the present invention provides a curable composition comprising a cyanoacrylate component and a solid thermoplastic polyether polyurethane resin, wherein the solid thermoplastic polyether polyurethane resin has a molecular weight, Mw, in the range of about 180,000 g / mol to about 260,000 g / mol, where Mw is measured according to ASTM D5296-05.

[0038] Surprisingly, it has been found that by combining a solid thermoplastic polyether polyurethane resin with a curable cyanoacrylate component, films with very high integrity can be produced.

[0039] The solid thermoplastic polyether polyurethane resin used in the curable compositions of the present invention may be present in an amount greater than about 50 weight percent, based on the total weight of the composition. Without wishing to be bound by any theory, it is believed that this relatively high proportion of thermoplastic polyether polyurethane resin in the composition may contribute to the high integrity of films formed by the composition.

[0040] Thermoplastic polyether polyurethane resins have shown excellent stability in a wide variety of cyanoacrylate monomers.

[0041] Thermoplastic polyether polyurethane resins have mechanical properties intermediate between thermoplastic and thermoset materials. This is achieved through "virtual crosslinks" created by hydrogen bonding between urethane groups on opposing polymer chains. This interchain hydrogen bonding gives these unusual materials a wide range of physical properties, which manifest macroscopically in the form of excellent elasticity and elongation.

[0042] These rubbery or elastic properties allow for the production of films with very high integrity.

[0043] Additionally, thermoplastic polyether polyurethane resin film formers have excellent tensile strength and elongation properties, offering advantages over other available film formers.

[0044] The use of liquid cyanoacrylate monomers is believed to allow for better diffusion into the bulk than solid cyanoacrylate monomers, resulting in faster cure at room temperature.

[0045] When solid thermoplastic polyether polyurethane resins are combined with liquid cyanoacrylate monomers, the resulting films not only have high internal structural integrity but also cure rapidly upon contact with standard substrates.

[0046] Suitable solid thermoplastic polyether polyurethane resins for use in the present invention have a molecular weight Mw in the range of about 180,000 g / mol to about 260,000 g / mol. Suitably, the solid thermoplastic polyether polyurethane resin has a molecular weight Mw in the range of about 200,000 g / mol to about 240,000 g / mol, such as about 215,000 g / mol to 230,000 g / mol, e.g., 220,000 g / mol to 225,000 g / mol, e.g., about 223,000 g / mol, where Mw is measured according to ASTM D5296-05. The solid thermoplastic polyether polyurethane resin may have a melting point of 160°C to 200°C, e.g., 165°C to 190°C, e.g., 170°C to 180°C. Suitable solid thermoplastic polyether polyurethane resins include Pearl Bond® 960, available from Lubrizol (Gran Vial Street 17, Montmeló, Barcelona, ​​Spain, 08160). Pearl Bond® 960 is a solid thermoplastic polyether polyurethane resin with a Mw of 222,906, as measured in accordance with D5296-05 (Standard Test Method for Molecular Weight Average and Molecular Weight Distribution of Polystyrene by High Performance Size Exclusion Chromatography), and a melting point in the range of 170°C to 180°C.

[0047] The formulation of the compositions and products of the present invention can be achieved by mixing a solid thermoplastic polyether polyurethane resin with a solvent and stirring at an elevated temperature. Preferably, the mixture is stirred at an elevated temperature, e.g., about 65°C. The actual temperature used may vary depending on the melting point or solubility of the TPU used. Mixing is performed for a time sufficient to dissolve the TPU component in the solvent, which may vary depending on the batch size. At this stage, a stabilizer may be added. Next, the cyanoacrylate component is added to the composition. While not wishing to be bound by any theory, it is believed that adding the cyanoacrylate component later has a beneficial effect on the stability of the final product.

[0048] The adhesive formulation can be applied to a substrate, such as a release liner, optionally by casting. The substrate can be left at an elevated temperature, such as about 60°C, for example, for about 5 minutes to facilitate solvent removal. After this period, the film thickness can be substantially less than that of the wet coating. Once the solvent has evaporated, the film can be quickly rolled up to prevent dust particles or moisture from contacting the surface of the film.

[0049] Suitably, the compositions of the present invention may be provided in any suitable solid form, such as a tape, a filament, or a coating applied to a substrate, including filaments or threads made of other materials, such as nylon or polyester threads. A solid composition, such as a tape or filament, may have sufficient integrity to be handled without breaking. A solid composition, such as a tape or filament, may be applied to a substrate, such as a metal bolt, at room temperature. A solid composition, such as a tape or filament, may be heat-resistant to temperatures of at least 150°C, e.g., 180°C. This means that the composition is robust enough to maintain performance at temperatures typical of industrial environments. Even at high temperatures, a solid composition, such as a tape or filament, is non-tacky and dry to the touch, eliminating the need for a carrier such as a release liner. A tape or filament composition is wound on itself and, because it is non-tacky and dry to the touch, does not adhere to itself. Alternatively, a tape or filament may comprise the curable composition described herein and one or more release liners. For example, a release liner may be useful if the composition is stored at temperatures above 40° C., as a non-tacky composition may become tacky and stick to itself at temperatures above 40° C. As noted above, the compositions of the present invention may be in any suitable solid form, such as a tape, filament, or coating (solid, dry to the touch) that is applied to a substrate, including, for example, a filament or yarn made from another material, such as nylon or polyester yarn.

[0050] Definitions and Standard Test Methods As used herein, the term "liquid" means in a liquid state within a temperature range of about 5°C to 30°C, suitably at room temperature and atmospheric pressure.

[0051] As used herein, the term "solid" means in the solid state within a temperature range of about 5° C. to 40° C., and suitably at room temperature and atmospheric pressure. The solid state is defined as a state of matter in which the material is not fluid, maintains boundaries without support, and the atoms or molecules occupy fixed positions relative to one another and are not free to move.

[0052] As used herein, the word "tape" refers to an article comprising a curable composition and one or more release liners.

[0053] As used herein, the phrases "stabilizer" or "Lewis acid stabilizer" refer to a substance that stabilizes a curable cyanoacrylate component, for example, by inhibiting premature polymerization of the cyanoacrylate. Examples of such substances include boron trifluoride (BF) or sulfur dioxide (SO). Those skilled in the art will readily recognize that other suitable stabilizers, such as other suitable Lewis acids, can be used to stabilize the curable cyanoacrylate component. It has been disclosed that stabilizer solutions can be prepared using ethyl cyanoacrylate, β-methoxy cyanoacrylate, or butyl cyanoacrylate as a stabilizer carrier, and the stabilizer solutions are suitable for adjusting the amount of stabilizer in curable compositions based on ethyl cyanoacrylate, β-methoxy cyanoacrylate, or butyl cyanoacrylate, respectively.

[0054] In the context of the present invention, non-tacky means that the composition is dry to the touch but does not peel off during handling or use. For example, an article coated with the composition of the present invention is dry to the touch. An article coated with the composition of the present invention is considered dry to the touch if 20 such articles are individually placed on dry tissue paper for 4 hours without any change in the appearance of the tissue paper.

[0055] Molecular weights disclosed herein were determined in accordance with ISO 13885-1:2008, "Binders for paints and varnishes -- Gel permeation chromatography (GPC) -- Part 1: Tetrahydrofuran (THF) as eluent."

[0056] The melting and re-solidification temperature ranges were measured according to ISO 1137-1:2016 "Plastics - Differential scanning calorimetry (DSC) - Part 1 General principles." [Example]

[0057] Exemplary compositions of the present invention may be those shown in Table 1. [Table 1]

[0058] The compositions of Table 1 may be prepared as follows.

[0059] In a suitable container, the solid thermoplastic polyether polyurethane resin is dissolved in a solvent such as ethyl acetate. The mixture is brought to a suitable temperature, e.g., about 65°C, and stirred until the solid thermoplastic polyether polyurethane resin is completely dissolved. The stabilizer is then added, followed by the relevant cyanoacrylate monomer.

[0060] As used herein in relation to the present invention, the words "comprise" and "have / comprise" are used to specify the presence of features, integers, steps or components, but do not exclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

[0061] It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.

Claims

1. a cyanoacrylate component, and solid thermoplastic polyether polyurethane resin, A curable composition comprising: A curable composition wherein said solid thermoplastic polyether polyurethane resin has a molecular weight Mw ranging from about 180,000 g / mol to about 260,000 g / mol, said molecular weight Mw being measured according to ASTM D5296-05.

2. 2. The composition of claim 1, wherein the solid thermoplastic polyether polyurethane resin has a molecular weight Mw in the range of about 200,000 g / mol to about 240,000 g / mol, such as about 215,000 g / mol to 230,000 g / mol, for example, 220,000 g / mol to 225,000 g / mol, for example, about 223,000 g / mol, wherein the molecular weight Mw is measured according to ASTM D5296-05.

3. 3. The composition of claim 1 or 2, wherein the solid thermoplastic polyether polyurethane resin has a melting point of from 160°C to 200°C, such as from 165°C to 190°C, for example from 170°C to 180°C.

4. The composition of any one of claims 1 to 3, wherein the cyanoacrylate component is a liquid curable cyanoacrylate component.

5. The composition of any one of claims 1 to 4, wherein the cyanoacrylate component is selected from the group comprising ethyl cyanoacrylate, butyl cyanoacrylate, β-methoxy cyanoacrylate, and combinations thereof.

6. 6. The composition of any one of claims 1 to 5, wherein the solid thermoplastic polyether polyurethane resin is present in an amount of from about 25% to about 90% by weight based on the total weight of the composition, suitably in an amount greater than 50% by weight, for example from about 65% to about 85% by weight based on the total weight of the curable composition.

7. 7. The composition of any one of claims 1 to 6, wherein the cyanoacrylate component is present in an amount of about 10 wt% to about 75 wt% based on the total weight of the composition, for example, in an amount of about 15 wt% to 35 wt% based on the total weight of the curable composition.

8. The composition of any one of claims 1 to 7, further comprising from about 5 ppm to about 200 ppm, for example from about 10 ppm to about 100 ppm, of a stabilizer for the cyanoacrylate component.

9. The stabilizer is boron trifluoride (BF ３ ) or sulfur dioxide (SO ２ 9. The composition of claim 8, wherein the compound is selected from the group consisting of:

10. The stabilizer is sulfur dioxide (SO ２ 10. The composition of claim 9, wherein

11. The composition of any one of claims 1 to 10, further comprising a solvent selected from the group comprising ethyl acetate, tetrahydrofuran, methyl ethyl ketone, cyclohexanone, and acetone.

12. 12. The composition of claim 11, wherein the solvent used is ethyl acetate.

13. The composition of any one of claims 1 to 12 provided in the form of a tape, filament, or coated substrate.

14. The composition according to any one of claims 1 to 13, provided in the form of a tape.

15. A tape comprising the curable composition of any one of claims 1 to 14 and one or more release liners.

16. i) combining a solid thermoplastic polyether polyurethane resin component according to any one of claims 1 to 12, a cyanoacrylate component according to any one of claims 1 to 12, and a solvent to form a mixture; ii) applying the mixture of step (i) to a substrate, optionally by casting; iii) evaporating the solvent or actively removing the solvent, thereby forming a solid curable composition; A method for preparing a curable composition comprising:

17. The method of claim 16, wherein the substrate is a release liner.

18. 18. The method of claim 16 or 17, wherein the solvent is ethyl acetate.

19. 19. The method of any one of claims 16 to 18, wherein the solid thermoplastic polyether polyurethane resin is present in the curable composition in an amount greater than about 50 wt%, the wt% being based on the total weight of the composition.

20. The curable composition of any one of claims 1 to 14 in cured form.

21. An assembly comprising two substrates bonded by the curable composition of any one of claims 1 to 14 in cured form.

Images