JP2004528484A - High mechanical performance glove with high resistance to chemical products and / or radiolysis and method of making the same - Google Patents

Abstract

The present invention relates to a glove with high mechanical performance and high resistance to chemical products and / or radiolysis, which is the same, obtained from a solution of an elastomer in one or several organic solvents or in water. Or characterized by including one or several elastomer layers, which are reinforced with a fabric having high mechanical strength on one or several parts or all of the inner surface of the glove Has been. The invention also relates to a method of making the glove and its use.

Description

【Technical field】
[0001]
The present invention relates to gloves that exhibit high mechanical performance with high chemical and radiolytic resistance, and processes for producing such gloves.
[0002]
Various types of gloves have been described for application in the nuclear industry.
[0003]
In particular, US Pat. No. 5,165,114 under the name Siemens AG discloses a glove that is particularly suitable for mounting in a glove box containing radioactive material. These gloves are layers formed from a mixture of polyurethane layer, rubber layer (eg chlorosulfonated polyethylene or ethylene-propylene copolymer), lead oxide and polychloroprene (for radioactivity protection) from the inner surface to the outer surface of the globe. Then, again, a rubber layer and a polyurethane layer are formed from a superposition of rubber layers that prevent the polyurethane from reacting with lead oxide. These gloves are suitable for protection against radiation, but do not have sufficient mechanical properties.
[0004]
Furthermore, French patent application 2 777 163 in the name of Piercan SA discloses a glove comprising a rubber layer (eg butyl rubber) and a polyurethane layer designed to come into contact with the human hand. The latter provides a glove with mechanical strength, but the rubber layer present on the inner surface of the glove prevents hydrolysis of the polyurethane when in contact with the user's hand. Such a glove can be used especially in a glove box for handling radioactive substances. They have a tear strength of 24N and a puncture strength of 55N according to the NF EN 388 Standard.
[0005]
However, gloves suitable for handling such radioactive materials do not exhibit sufficient mechanical properties. In particular, these puncture and tear strengths do not provide optimal protection for the user.
[0006]
On the other hand, a glove that provides a high protection against the risk of cutting is disclosed in EP 0 716 817 under the name Hutchinson. These gloves contain a high cut-resistant material (eg para-aramid fiber knit) on the surface of the glove intended to cover the palm, but the surface of the glove intended to cover the back of the hand is natural or synthetic Formed by an elastic fabric of organic fibers (eg cotton fiber knit). On all or part of its outer surface, the glove is used to make the fibers impervious to certain drugs (eg oils or aqueous substances) and when objects with ridges are handled. To prevent premature wear or degradation of the fiber, it can be coated with an elastomer by continuously immersing the glove in the aqueous dispersion of the elastomer.
[0007]
Apart from their role in making the fabric impermeable and protecting it from the external environment in order to efficiently protect the user's hand, it exhibits excellent mechanical properties, especially in terms of puncture strength and tear strength It would be desirable to use an elastomer. In this regard, it is more advantageous to use an elastomer derived from a solution, which may have better mechanical properties than if derived from an aqueous dispersion (eg in the case of certain polyurethanes). Furthermore, certain elastomers can be used only in the form of a solution and are therefore not available in the form of an aqueous dispersion, as is the case for example with butyl rubber.
[0008]
Currently EP 0 716 817 discloses coating the fabric only with an elastomer in the form of an aqueous dispersion by continuously dipping the fabric in these aqueous dispersions. As known to those skilled in the art, it is practically excluded to immerse the fabric directly in the elastomer solution. This is because the high osmotic power of the elastomer solution entails the inclusion of a complete fabric across its entire thickness in the elastomer. This results in a loss of fabric flexibility. In this way, the resulting gloves are particularly uncomfortable for the user to wear, and their lack of flexibility makes them unsuitable to accompany hand and finger movements.
[0009]
Similarly, U.S. Pat. No. 4,742,578 discloses a surgical glove formed from a synthetic rubber latex layer to which a fabric coating is bonded and bonded. The manufacture of these gloves is performed in two steps:
1) A step of immersing a mold in latex, and then drying and vulcanizing;
2) A process of bonding and bonding a part of the fabric to a sensitive part.
[0010]
In this way, the resulting glove can be dipped again in the latex. This can also be reversed. The mechanical strength and chemical resistance of these gloves are insufficient. Furthermore, resistance to radiation is neither mentioned nor suggested in the literature.
[0011]
Finally, US Pat. No. 5,259,069 discloses a surgical glove formed from an inner glove made from an elastic material, the inner glove being sealed in place with respect to the inner glove. Covered with a second glove made from, part of the fabric is located between the two elastic gloves and these parts of the fabric can move between the two gloves. The literature teaches the preparation of gloves by immersing the mold in a latex bath. These gloves show insufficient chemical resistance and mechanical strength, and resistance to radiation is not mentioned or suggested in this document.
DISCLOSURE OF THE INVENTION
[Problems to be solved by the invention]
[0012]
In view of the shortcomings of the gloves disclosed in the prior art, the object of the present invention is to provide a glove that exhibits high mechanical performance, particularly with respect to puncture strength and tear strength, yet is suitable for handling radioactive materials and / or chemicals It is to be.
[Means for Solving the Problems]
[0013]
These objectives are achieved by combining a high strength fabric layer with one or more elastomer layers selected for their high chemical resistance and / or their radiolysis resistance. What is used for this purpose is surprisingly elastomers in the form of solutions in one or more organic solvents or in water, which are of a type that is not known to the person skilled in the art in combination with fabrics. It is an elastomer.
[0014]
The subject of the present invention is therefore a glove exhibiting high mechanical performance with high chemical and / or radiolytic resistance, characterized by comprising:
One or more elastomer layers obtained from a solution of elastomers in the same or different one or more organic solvents or in water,
-These layers that are reinforced over one or more parts or the whole of the inner surface of the glove by a high-strength fabric.
[0015]
In the context of the present invention, the term “radiolysis-resistant glove” means that degradation due to the action of radiation (mainly without the appearance of cracking in the structure of the glove) is months after use (at least after 3 months, advantageously) Is understood to mean a glove that is not visually detectable after 12-36 months or more).
[0016]
The term “chemically resistant glove” refers to the handling of substances that the user must avoid any contact (eg, substances that attack the skin or that are dangerous to contact (eg, virus preparations, corrosive chemicals)). It is understood to mean a glove that allows.
[0017]
The term “elastomer solution” is understood to mean an elastomer in liquid form that exists as a single continuous phase for an aqueous elastomer dispersion (or latex).
[0018]
The term “inner surface of the glove” is understood to mean the surface of the glove intended to come into contact with the user's hand.
[0019]
The term “high-strength fabric” is understood to mean a fabric having a high puncture strength and a high tear strength, which are determined according to NF EN 388 Standard. Regarding the level of cut resistance, this depends on the nature of the fabric selected, the fiber diameter and the mesh size of the fabric when the fabric fibers are knitted.
[0020]
According to NF EN 388 Standard, the level of puncture strength, cut resistance and tear strength includes different mechanical properties. Because they are resistant to various types of mechanical stress, mainly to contact with sharp objects, to contact with objects to cut, and not torn further from this notch of specimens with notches Because it corresponds to each ability.
[0021]
In the glove according to the invention, the high-strength fabric is advantageously woven, selected from high-strength polyethylene, high-strength polyester, polyaramid (eg KEVLAR®), polyamide, viscose and mixtures thereof. Made of natural or synthetic fibers, either knitted or knitted.
[0022]
The elastomer itself may be polyurethane, chlorosulfonated polyethylene (eg, a product sold under the trade name HYPALON® by DuPont de Nemours, France), polychloroprene (eg, trade name NEOPRENE by DuPont de Nemours, France). Products sold under the registered trademark), butyl rubber, synthetic or natural polyisoprene, polyvinyl alcohol and mixtures thereof may be selected.
[0023]
However, these examples are not limiting: In general, any elastomer can be used that can be dissolved in an organic solvent or in water and that allows the formation of a film after evaporation of the solvent.
[0024]
The fact that they use elastomers in the form of a solution [or (for example in the case of polychloroprene) use an elastomer that belongs to the same chemical family but has a different structure than that present in the form of an aqueous dispersion] It advantageously makes it possible to select an elastomer that has better mechanical properties than if derived from an aqueous dispersion (for example in the case of certain polyurethanes). Furthermore, certain elastomers are not available in the form of an aqueous dispersion, but can only be used in the form of a solution (eg in the case of butyl rubber).
[0025]
Depending on the nature of the elastomer chosen, the glove according to the invention may exhibit high chemical and / or radiolytic resistance in addition to high mechanical performance. Taking examples from the aforementioned elastomers, the use of polyurethane, chlorosulfonated polyethylene and polychloroprene makes it possible to obtain radiolysis-resistant gloves. Chlorosulfonated polyethylene, polyvinyl alcohol and polyisoprene (including natural rubber) also confer excellent chemical resistance to liquids (water, oil, solvent) on the gloves according to the present invention. If chemical resistance to gas is desired, the use of butyl rubber is recommended.
[0026]
In one advantageous embodiment of the glove according to the invention, this includes:
One or more layers of polyurethane obtained from a solution of said polyurethane in one or more organic solvents,
-These layers that are reinforced by high strength fabrics covering one or more or all of the inner surface of the glove.
[0027]
Preferably, the polyurethane solution includes at least one polar solvent.
[0028]
Such gloves are resistant to radiolysis and can therefore be used in a radioactive environment.
[0029]
In the glove according to the invention, the total thickness of the elastomer layer is preferably between 0.3 and 1 mm.
[0030]
Regardless of the nature of the elastomeric layer, the glove according to the invention advantageously has a puncture strength of at least 150 N and a tear strength of at least 75 N, which are measured according to NF EN 388 Standard (ie this Level 4 puncture and tear strength according to standard).
[0031]
The glove according to the invention also has excellent resistance to thermal aging and is completely impermeable within the meaning of NF EN 374-2 Standard.
[0032]
The subject of the present invention is also a process for manufacturing said glove characterized in that it comprises the following steps:
a) immersing the mold at least once in one or more identical or different solutions of one or more elastomers in one or more organic solvents or in water;
b) applying a high strength fabric layer to one or more or all of the surface of the elastomeric layer as obtained from the previous step;
c) removing the glove by turning it over.
[0033]
In this process, organic solvents and high strength fabrics are defined above with respect to the glove according to the present invention.
[0034]
Depending on the desired final thickness of the elastomer layer, step a) of immersing the mold in the elastomer solution can be repeated up to 20 times (eg 6 to 20 times). In this case, each elastomer layer is at least partially dried before the mold is immersed again in the elastomer solution.
[0035]
The process according to the invention may comprise a step a ′) of drying each elastomer layer obtained for the mold during step a) before step b).
[0036]
According to one advantageous method of carrying out the process according to the invention, the high-strength fabric layer applied during step b) is in water optionally containing a nonionic surfactant or with the fabric layer Pre-impregnated with at least one solvent for the elastomer in direct contact.
[0037]
As a variant, the process according to the invention comprises between step b) and c) a step b ′) in which a high-strength fabric layer is impregnated with at least one solvent for the elastomer in direct contact with said fabric layer. Can do.
[0038]
Impregnation of the fabric with a solvent can be performed, for example, by applying the solvent to the fabric layer by brushing or by spraying. This impregnation can also be carried out by immersing any of the following in at least one solution for the elastomer:
A mold / elastomer / high strength fabric assembly, if impregnation of the fabric with solvent is carried out between steps b) and c); or
If the impregnation of the fabric with a solvent is carried out before step b), the fabric alone.
[0039]
The solvent used to impregnate the fabric allows the latter to be bonded to the elastomeric layer: this allows the surface of the elastomer in contact with the fabric to partially dissolve, This results in adhesion at the interface between the elastomer and the fabric.
[0040]
The process according to the invention preferably includes a step c ′) of drying the mold / elastomer / high-strength fabric assembly just prior to the step c) of removing the glove by turning it over.
[0041]
As mentioned above, in view of the various features of the process according to the present invention, this may include the following sequence of steps:
a) immersing the mold at least once in one or more identical or different solutions of one or more elastomers in one or more organic solvents or in water;
a ′) drying each elastomer layer obtained for said mold during step a);
b) applying a high-strength fabric layer to one or more or all of the surface of the elastomer layer as obtained after the previous step, the fabric possibly containing a non-ionic surfactant A process that can absorb water, if necessary;
b ′) impregnating the high strength fabric layer with at least one solvent for the elastomer in direct contact with the fabric layer;
c ′) drying the mold / elastomer / high strength fabric assembly obtained after the previous step;
c) removing the glove by turning it over.
[0042]
The process according to the invention may also comprise a sequence of the following steps:
a) immersing the mold at least once in one or more identical or different solutions of one or more elastomers in one or more organic solvents or in water;
a ′) drying each elastomer layer obtained for said mold during step a);
b) applying a high-strength fabric layer to one or more parts or the entire surface of the elastomer layer as obtained after the previous step, at least one for the elastomer with which the fabric is in direct contact with the fabric layer. Impregnating with two solvents;
c ′) drying the mold / elastomer / high strength fabric assembly obtained after the previous step;
c) removing the glove by turning it over.
[0043]
The elastomer used in the process according to the invention may be selected from the group formed by polyurethane, chlorosulfonated polyethylene, polychloroprene, butyl rubber, synthetic or natural polyisoprene, polyvinyl alcohol and mixtures thereof.
[0044]
The process according to the invention makes it possible to reinforce one or more elastomer layers from a solution of said elastomer in an organic solvent or in water by means of a fabric. Such a process alleviates the disadvantages of previously known glove manufacturing processes.
[0045]
This is because the elastomeric layer derived from a solution of the elastomer in an organic solvent or in water is reinforced with the fabric and coats all the fibers of the fabric (thus causing loss of fabric flexibility). This is because no method has been described in the prior art that makes it possible to do this: the proposed method absorbs a fabric placed on a mold of the desired shape with a coagulation solution and then an aqueous elastomer dispersion Soaking the fabric in the body. This elastomer dispersion coagulates on the surface of the fabric without penetrating its entire thickness, as described, for example, in EP 0 716 817. A step for removing the coagulation solution is then necessary before the glove is vulcanized and withdrawn from the mold.
[0046]
Other methods, including making the glove "inside out" (ie, forming an elastomeric layer and then bonding the fabric to these surfaces using an adhesive or lubricant) are also described in US Pat. No. 4,283,244, which requires the use of an elastomer in the aqueous dispersion.
[0047]
Particularly advantageously, therefore, the process according to the invention makes it possible to produce gloves comprising an elastomeric layer derived from a solution of said elastomer by means of a dipping technique, these layers being reinforced with fabric layers. . The novel sequential steps in the process according to the invention allow for limited interpenetration between the elastomer and the fabric when these two materials are brought into contact with each other during the process of step b). The elastomer only partially penetrates the thickness of the high strength fabric layer, preventing all the mesh of the fabric from being coated with the elastomer. Thus, the fabric remains flexible and retains its mechanical properties. This is a glove that is very flexible and comfortable to wear, gaining the essential properties that allow the user to perform meticulous tasks while maintaining very precise movements Make it possible.
[0048]
In particular, it should be noted that in accordance with the present invention, it is possible to produce a glove without any adhesive product involved in securing the fabric to the elastomer. This is an important advantage when the glove is used to handle radioactive material. This is because adhesive products are generally sensitive to radiolysis. When the glove is formed from a fabric and an elastomer that are bonded together by an adhesive, the degradation of the adhesive by radiolysis tends to cause the glove to lose its protective properties.
[0049]
Furthermore, the glove according to the present invention allows the human hand to be fully protected and allows the human hand to maintain all its dexterity when handling objects. Have
[0050]
The subject of the present invention is also the use of a glove as described above for handling radioactive substances or hazardous chemicals (eg corrosive chemicals) or biological materials.
[0051]
The subject of the present invention is also a glove box characterized in that it contains at least one glove as described above, i.e. a product that needs to be separated from the external environment, or in contact with a user or handler. It is a sealed enclosure for handling non-reliable products.
[0052]
Apart from the above provisions, the present invention also encompasses other provisions that will become apparent from the following description, which refers to detailed examples of the production of gloves according to the present invention. It should be understood, however, that these examples are provided merely to illustrate the subject matter of the present invention and that they do not show their limitations in any way.
BEST MODE FOR CARRYING OUT THE INVENTION
[0053]
Example: Production of a radiolysis-resistant glove according to the invention
A glove according to the present invention comprising a polyurethane layer reinforced with a fabric layer (ie DYNEEMA® (a high strength polyethylene fabric sold by DSM)) was obtained by the process described below.
[0054]
First, a step of immersing a mold having a hand shape and dimensions in a polyurethane solution of an organic solvent (eg, N, N-dimethylacetamide, dimethylformamide or tetrahydrofuran) or a mixture of several organic solvents was performed. .
[0055]
Any polyurethane known to those skilled in the art that can dissolve in organic solution and form a film after evaporation of the solvent can be used. By way of example, mention may be made of aromatic or aliphatic polyurethane, polyester or polyether types. However, these examples are not limiting, apart from the solubility characteristics and the film-forming properties described above, 20% elongation less than 3 MPa, modulus at 100% elongation less than 7 MPa, and tensile strength greater than 20 MPa. And any polyurethane having an elongation at break greater than 400% may be used.
[0056]
For molds, this can conventionally be made from ceramic or metal.
[0057]
Soaking the mold in the polyurethane solution is repeated 6 to 20 times, and each polyurethane layer obtained for the mold is, for example, between 20 and 130 ° C. before soaking the mold again in the polyurethane solution. Dry partially in oven at temperature (preferably 60 ° C.) for a time between 1 and 300 minutes (preferably 60 minutes). The temperatures and times indicated here depend on the solvent used and the type of polyurethane used.
[0058]
During each dipping operation, the mold was maintained in the polyurethane solution for 3 to 30 minutes (preferably 10 minutes).
[0059]
The polyurethane layer thus obtained for the mold is immersed in the latter one or more times in the polyurethane solution and then, for example, at a temperature between 20 and 130 ° C. (preferably 80 ° C.) for 2 to 24 hours. Completely dried in the oven for a period of time (preferably 5 hours). Both the temperature and time selected depend on the solvent used and the type of polyurethane used.
[0060]
A high strength fabric (in this case DYNEEMA®) absorbed water, which optionally contained up to 50% non-ionic (eg ethoxylated) surfactant. This fabric is applied to one or more parts or the entire surface of the polyurethane layer as obtained above, the application of the fabric to the polyurethane depending on the presence of water in the fabric and possibly a surfactant. Made easy by the presence of.
[0061]
For example, the fabric can be applied only to a portion of the polyurethane layer corresponding to the user's hand without covering a portion of the polyurethane layer corresponding to the user's forearm. It is also possible to apply the fabric in a number of well-defined areas on the polyurethane layer (eg in the area corresponding to the inner surface of the hand, in the area of the palm and along the area corresponding to the user's finger). It is also possible.
[0062]
The solvent for the polyurethane is then impregnated with DYNEEMA (for example, by impregnating the mold / polyurethane / high strength fabric assembly in at least one solvent for the polyurethane (N, N-dimethylacetamide, dimethylformamide or tetrahydrofuran). Applied in contact with the registered trademark layer.
[0063]
Drying the mold / polyurethane / high strength fabric assembly obtained above at a temperature between 20-100 ° C. (preferably 70 ° C.) will cause the fabric to adhere to the polyurethane at the interface between these two materials Made possible. The solvent for the polyurethane applied in contact with the DYNEEMA® layer can actually cause partial dissolution of the surface of the elastomer, thereby adhering to the fabric, and the fabric and polyurethane layer Adhere completely to each other after complete evaporation.
[0064]
Finally, it was removed from the mold by simply turning the glove over. A glove that was resistant to radiolysis for at least 24 months was obtained.
[0065]
In the example of the production of the radiolysis resistant glove described above, first using the same protocol described above in connection with the polyurethane, in a solution of the elastomer selected for its chemical resistance properties. It is also possible to immerse the mold and then immerse the mold in a solution of polyurethane or another radiolysis resistant elastomer before applying the high strength fabric to the polyurethane layer. In this way, a glove according to the invention comprising two different elastomeric layers (this glove is resistant to both radiolytic and chemical) is obtained.
[0066]
As is apparent from the above, the present invention is in no way limited to its method of implementation, its embodiments or more clearly described applications; on the contrary, the present invention may be within the ability of those skilled in the art. All modifications are encompassed and do not depart from the context or scope of the present invention.

Claims (19)

Less than:
One or more elastomer layers that are the same or different and are obtained from an elastomer solution in one or more organic solvents or in water;
-These layers that are reinforced by high strength fabrics covering one or more or all of the inner surface of the glove;
Gloves exhibiting high mechanical performance with high chemical and / or radiolysis resistance, characterized by containing 2. A glove according to claim 1, characterized in that the elastomer is in the form of a solution in one or more organic solvents or in water, present as a single continuous phase. Glove according to claim 1 or 2, characterized in that it comprises a high-strength fabric on the surface of the glove intended to come into contact with the user's hand. The high-strength fabric is from woven or knitted natural or synthetic fibers selected from high-tenacity polyethylene, high-strength polyester, polyaramid, polyamide, viscose and mixtures thereof. The glove according to any one of claims 1 to 3, wherein Any of claims 1-4, characterized in that the elastomer is selected from the group formed by polyurethane, chlorosulfonated polyethylene, polychloroprene, butyl rubber, synthetic or natural polyisoprene, polyvinyl alcohol and mixtures thereof. The globe according to claim 1. Less than:
One or more layers of polyurethane obtained from a solution of polyurethane in one or more organic solvents,
-These layers that are reinforced over one or more parts or the whole of the inner surface of the glove by a high-strength fabric.
The glove according to any one of the preceding claims, characterized by comprising: Glove according to any one of the preceding claims, characterized in that the total thickness of the elastomer layer is between 0.3 and 1 mm. Glove according to any one of the preceding claims, characterized in that it has a puncture strength of at least 150N. 9. A glove according to any one of the preceding claims, characterized in that it has a tear tear strength of at least 75N. a) immersing the mold at least once in one or more identical or different solutions of one or more elastomers in one or more organic solvents or in water;
b) applying a high strength fabric layer to one or more or all of the elastomer layer as obtained from the previous step; and c) including removing the glove by turning it over. A process for manufacturing a glove according to any one of the preceding claims characterized in that it is characterized. 11. Process according to claim 10, characterized in that the adhesive product does not require the fabric to be fixed to the elastomer. 12. A process according to claim 10 or claim 11, comprising a step a ') of drying each elastomer layer obtained on the mold during step a) before step b). process. The high-strength fabric layer applied during step b) is pre-impregnated with water optionally containing a nonionic surfactant or with at least one solvent for the elastomer in direct contact with the fabric layer. 13. Process according to any one of claims 10 to 12, characterized in that it is pre-impregnated. Between step b) and step c), comprising impregnating a high-strength fabric layer with at least one solvent for the elastomer in direct contact with the fabric layer, b ') The process according to any one of 10 to 13. 15. The method according to any one of claims 10 to 14, characterized in that it comprises the step of drying the mold / elastomer / high-strength fabric assembly just before step c) of removing the glove by turning it over. process. The elastomer according to claims 10-15, characterized in that the elastomer is selected from the group formed by polyurethane, chlorosulfonated polyethylene, polychloroprene, butyl rubber, synthetic or natural polyisoprene, polyvinyl alcohol and mixtures thereof. A process according to any one of the preceding claims. Use of a glove according to any one of claims 1 to 9 for handling radioactive substances. Use of a glove according to any one of the preceding claims for handling hazardous chemicals (e.g. corrosive chemicals) or biological materials. A glove box comprising at least one glove according to any one of claims 1-9.