JP2001522921A - Elastic articles from mixtures of polychloroprene and acrylonitrile - Google Patents

Abstract

  (57) [Summary] Molded resilient products such as gloves, condoms and breathing bags can be used to provide from about 10 parts to about 90 parts by weight of chloroprene polymer and from about 10 parts to about 90 parts by weight of nitrile based on 100 parts by weight of total polymer. Made from a polymer blend composition having a polymer. A molded resilient product, such as gloves, condoms, and breathing bags, comprises from about 10 parts to about 90 parts by weight of a chloroprene polymer and from about 10 parts to about 90 parts by weight, based on 100 parts by weight of total polymer. Made from a polymer blend composition having parts by weight of the nitrile polymer. The cured product is 0.05 to 50 mils thick, has a tensile strength of at least 9 MPa and an elongation of at least 300%. When stretched to fit a human body part, such as a hand, the product is subjected to an initial pressure, but then relaxes to a reduced pressure of 50% or more of the initial pressure. The present invention provides a mixture of polychloroprene and a nitrile polymer that produces a product having an equivalent or similar feel and functionality compared to conventional natural rubber latex gloves. These products feel equivalent or better than currently available nitrile or vinyl gloves.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to molded resilient products, particularly gloves, condoms and respiratory bags, and to polymer blend compositions useful in the manufacture of such products.

[0002]

[Description of Related Technology]

Elastic exercise equipment and surgical gloves, condoms and breathing bags, dip products (
For example, finger cots, catheters, balloons) and cast products (eg, tourniquets, sheet materials) have recently been made from several different polymers. Non-natural rubber latex products have been developed to solve the problems associated with natural rubber latex allergies. These recent materials lack the conforming properties required to serve as a suitable replacement for natural rubber latex. Furthermore, individual macromolecules have certain chemical compatibility issues, which limit their application in a wide range of markets, including health care, laboratory, emergency medical services and food processing.

[0003] Such surgical gloves are disclosed in US Pat. No. 5,014,362, Till.
This is described in US Pat. No. 5,014,362 to otson et al. Explained here
The glove that is used is a nitrile elastomer glove. More precisely, a "nitrile elastomer" is a carboxylated nitrile-butadiene elastomer. Tillotson gloves are relatively low resistant; made of such materials
When a worn glove is pulled, the stress exerted by the material (ie, the pressure or force per area) drops rapidly from its initial value. In other words, the material has a high permanent set.

[0004]

Summary of the Invention

The present invention provides a mixture of a polychloroprene and a nitrile polymer that provides a means having an equivalent or similar feel and functionality compared to conventional natural rubber latex gloves. These products are the same as currently available nitrile or vinyl gloves,
Offers excellent feel, comfort and ease of adaptation.

The present invention further provides a vulcanized or cured elastomer film obtained from the above-mentioned polymer and a molded product in the form of a film. Suitable molded products include gloves, condoms, breathing bags and other dip products.

[0006]

[Advantages of the present invention]

The polychloroprene and nitrile blend gloves, condoms and breathing bags of the present invention are made from synthetic elastomers and are free of allergic latex proteins. These are manufactured using methods similar to current manufacturing methods and techniques. The product is oxygen and ozone resistant. Such mixtures can form films with greater extensibility and faster thin film rebound as compared to currently available nitrile or vinyl products. This mixture is soft at low temperatures compared to currently available nitrile products. The mixture is also gas impermeable as compared to currently available natural rubber latex products.

[0007] The mixture is more gasoline and oil resistant than current polychloroprene. In addition, it has lower gas permeability than currently available natural rubber latex.

[0008] The tactile and physical properties of the elastomers and gloves of the present invention are similar to those of natural rubber latex and better than those of other latex-derived synthetic elastomers. The materials and products of the present invention have good chemical and puncture resistance, similar to those of other synthetic materials, and have better resistance than that of natural rubber latex. In essence, the materials and products of the present invention have all of the advantages of synthetic materials and products, for example, good chemical resistance, good puncture resistance and no known allergenicity, feel like natural rubber latex Having.

[0009] Materials and products, such as the gloves of the present invention, maintain a large percentage of the initial stress over time and maintain higher initial stresses than do nitrile elastomers and products made therefrom. In other words, they have little relaxation. Nitrile elastomers have high modulus and low resilience, and gloves made therefrom will tire hands. In contrast, gloves made from the elastomers of the present invention minimize hand fatigue. Nitrile elastomers also have permanent fixing properties,
Loses resistance and elasticity for a long time and withdraws. The material of the present invention is more like a natural rubber latex than a nitrile elastomer in this regard. Another advantage is that the materials and gloves of the present invention do not have an unpleasant odor, whereas nitrile gloves have an unpleasant odor that bothers the user and the patient (eg, a dentist patient). .

[0010] The objects and advantages of the present invention will be apparent from a reading of the following detailed description of the preferred embodiments when taken in conjunction with the drawings. FIG. 1 is a graph comparing stress versus time relaxation of the elastomer latex material of the present invention to a conventional elastomer latex material. FIG. 2 is a graph showing the puncture resistance of the conventional elastomer latex material and the elastomer latex material of the present invention.

[0011]

[Detailed description of preferred embodiments]

The present invention comprises elastomeric products such as gloves, condoms and breathing bags, especially composed of polychloroprene (or chloroprene polymer) and acrylonitrile copolymer. The terms "polychloroprene" and "chloroprene polymer" are used hereinafter to denote poly (2-chloro-1,3-butadiene) homopolymer and said 2-chloro-1,3-butadiene and at least one additional halogenated compound. Used to indicate both the monomer and the copolymer of the 2-chloro-1,3-butadiene.

Thus, 2-chloro-1,3-butadiene, known as chloroprene,
2,3-dichloro-1,3-butadiene or 2,3-dibromo-1,3-butadiene, 2-chloro-3-bromo-3,3-butadiene, 2-bromo-3-chloro-1,3- It can be copolymerized with one or more monomers selected from the group consisting of butadiene and butadiene. The acrylonitrile copolymer is preferably a carboxylated copolymer of acrylonitrile and butadiene. However, non-carboxylated acrylonitrile copolymers are also useful. Carboxylation is obtained by copolymerizing acrylonitrile and butadiene with a small amount (typically 10% or less) of an ester thereof, such as acrylic acid or methacrylic acid or methyl methacrylic acid.

The polymer mixture described herein, together with further components, is vulcanized or cured to form a thin film elastomer, as described below. The total mixed film thickness is about 0.05-50 mil, preferably about 0.1-20 mil. The mixed film is characterized in that it has a tensile strength of at least 9 MPA (equivalent or greater) and an elongation of equal to or greater than 300%, preferably at least 500%. . The product is also free from latex protein allergy, has low modulus, high elongation, high puncture resistance, good UV (ultraviolet) resistance, good chemical resistance and good film repellency Having.

The present invention also comprises a mixing step with a composition useful for making a mixed elastomeric product of the type described above.

The general composition of a non-vulcanized or non-cured polymer blend composition according to the present invention is shown in Table 1. The components other than the polymer blends shown in Table 1 are classic.

[0016]

[Table 1]

Prior to vulcanization, polymer mixing is performed.

In the practice of the present invention, the desired dip configuration is either in a single polymer mixed latex bath containing the polymer mixed composition as shown in Table 1 or in two separate polymer mixed dip baths. The first of the two separate polymer-mixed dip baths contains one of the polymers of the mixture (ie, polychloroprene) and the second
Contain other macromolecules (ie, acrylonitrile copolymers). The desired polymer mixture is formed on the dip form in the latter case. Single polymer mixtures are preferred. The dip form is dipped in the coagulation bath and dried before dipping in the latex bath, whether using a single latex bath or two latex baths. The latex-coated dip form is soaked in a warm water extraction bath if desired. Next, the latex-coated dip shape (or molded product)
Heat in an oven to cure the polymer-mixed latex.

The shape of the product from which the shape of the dip feature is obtained is determined. A polymer-mixed latex glove is obtained using a glove-shaped dip. Similarly, using a condom-shaped dip, a condom is obtained, and using a breathing bag-shaped dip,
A breathing bag is obtained. Instead, the films of the present invention are made by casting. Known casting techniques can be used.

The polymer mixture as shown in Table 1 has about 10 to about 90 parts by weight of polychloroprene (homopolymer or copolymer) and about 10 to 90 parts by weight of acrylonitrile copolymer, as described above.

The present invention comprises a mixture of about 10 to 90 parts by weight of polychloroprene (morphopolymer or copolymer) and about 10 to 90 parts by weight of acrylonitrile copolymer, having a tensile strength higher than 9 MPa and an elongation higher than 300%. Outlined as a resilient thin film product (such as gloves) consisting of a layer of resilient material. A preferred tensile strength is at least 12.5 MPa and a preferred elongation is at least 500%
It is.

The layer of resilient material, which is essentially impervious to water and water vapor, has a thickness that ensures that it conforms to the human body part and can be stretched to conform to the shape of the human body part. , Whereby an initial pressure is applied to the human body part, and one minute after extension,
The pressure is reduced to a pressure reduced to 0% or more, and a pressure reduced to 50% or more of the initial pressure is applied 10 minutes after the elongation. Further, this layer has a thickness of about 0.05 to 50 mils, and is preferably about 0.1 to 20 mils, which makes up the overall thickness of the product.

More preferably, the mixture comprises about 25-75 parts by weight of polychloroprene and about 25 parts by weight.
Contains ７５75 parts by weight acrylonitrile butadiene. More preferably, the polychloroprene is poly (2-chloro-1,3-butadiene) or 2-chloro-
1,3-butadiene and 2,3-dichloro-1,3-butadiene, 2,3-dibromo-1,3-butadiene, 2-chloro-3-bromo-1,3-butadiene or 2-bromo-3- One or more of chloro-1,3-butadiene and 1,3-butadiene. Acrylonitrile copolymer is a carboxylated copolymer of acrylonitrile and butadiene.

The elastic glove of the present invention has no latex protein allergen, low modulus, high elongation, high puncture resistance, high cut resistance, good UV (ultraviolet) resistance,
It has good chemical resistance and good thin film repulsion. Elastic membranes, condoms and breathing bags have these same properties.

The polymer blend elastomers of the present invention also have higher oil and chemical resistance (particularly against oils and non-polar hydrocarbons) than natural rubber latex, and
It has better exquisiteness than nitrile.

An important property of the resilient polymer-mixed thin films of the present invention and products made therefrom is that when subjected to a stress (or deformation) that is held constant over time,
To exhibit high stress retention (or low relaxation). The polymer mixed thin film or product of the present invention retains 60% or more of its initial stress after 1 minute and retains 50% after 10 minutes.

FIG. 1 shows the stress retention as a function of time (minutes) for the polymer blend elastomers of the invention (designated “NeoPro” in FIG. 1) and conventional nitrile, vinyl and natural rubber latex. (As% of initial stress). As shown in FIG.
The elastomer (NeoPro) of the present invention had better stress retention than any of the other synthetic polymers. Only natural rubber latex showed better stress retention. Disadvantages of natural rubber latex including allergic tendency include low puncture resistance and low oil resistance.

FIG. 2 shows the puncture resistance of the polymer blend elastomer of the present invention (designated “NeoPro”) and the prior art elastomers, ie, vinyl, natural rubber latex and nitrile. As shown in FIG. 1, the elastomer of the present invention (NeoPro) exhibits better stress relaxation than any of the other synthetic polymers. Only natural rubber latex showed better stress relaxation. It is well known that the disadvantages of natural rubber latex are low puncture resistance and low oil resistance, including allergic tendency.

[0029]

Example of the best mode known to the inventor]

Gloves can be manufactured as follows. A latex material having the composition shown in Table 2 is produced. Parts per hundred rubber are by weight and based on dry material.
Often, the materials are in liquid form at various weight percent solids. Sulfur is a crosslinker, zinc dibutyldithiocarbamate is an accelerator, zinc oxide is an accelerator and a curing agent, phenolic antioxidants are anti-deterioration agents, and potassium hydroxide is a pH stabilizer. Yes, stabilizing surfactants are stabilizers and wetting agents, and paraffin wax is a softening agent.

The clean porcelain molding is immersed in a coagulating liquid having calcium salts (eg, calcium, calcium chloride), water and a non-ionic surfactant and is reminiscent. Next, the molded product is immersed in the latex mixture (Table 2). The molded latex film is then extracted, dried, and cured for 20 minutes in a 235 F oven. After curing, the coated moldings are again extracted with hot water, then dipped in a slurry containing water and a slip agent and dried. Next, the glove is peeled from the molded product.

If a powderless product is desired, no further processing is required on the line.

[0032]

[Table 2]

Neoprene 750 is available from Dupont Dow Elastomers LLC (Wilmington, Del.)
obtained from aware). Tylac 68073 is Reichhold Chemical.
Inc., (Reserch Triangle Park, North Carolina).

The present invention has been described with reference to preferred embodiments, including the best mode and preferred embodiments. It should be understood that this is for the purpose of illustration, not limitation.

[Brief description of the drawings]

FIG. 1 is a graph comparing stress versus time relaxation of an elastomer latex material of the present invention versus a conventional elastomer latex material.

FIG. 2 is a graph showing puncture resistance of a conventional elastomer latex material and the elastomer latex material of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61L 31/00 C08L 11:00 C08L 11:00 A61F 5/43 (81) Designated countries 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, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ) , MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, E, ES, FI, GB, GE, GH, GM, HU, ID, IL, 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, U Z, VN, YU, ZW (72) Inventor Aldeep, Fortuneto, G USA 89523 Leno Shadow Park Drive, Nevada, USA 5811 (72) Inventor Glen, James, S. United States Nevada 89509 Leano Foster Drive, 1601 F term (reference) 4C081 AC10 AC13 BB07 BB08 CA121 CA122 CB051 CC01 CC05 DA02 DA03 DC12 4C098 AA06 DD14 DD22 EE11 4F071 AA12X AA13 AA34X AA76 AE02 BC01 4J002 AC07X AC09W BG10X DA047 EV156 FD147 FD156 GC00

Claims (25)

[Claims] (I) from about 10 parts by weight to about 90 parts by weight of a chloroprene polymer and
And (II) from about 10 parts to about 90 parts by weight of an acrylonitrile polymer; containing at least one crosslinking agent and at least one vulcanization accelerator; and having a tensile strength of at least 9 MPa and at least 300%. A polymer mixed composition characterized in that it can be cured into an elastomer in a thin film form having an elongation degree. 2. The composition of claim 1, wherein the composition comprises about 25 parts to about 75 parts by weight of a chloroprene polymer and about 25 parts to about 75 parts by weight of an acrylonitrile polymer. Molecular mixture composition. 3. The composition of claim 1, wherein the composition comprises about 40 parts to about 75 parts by weight of a chloroprene polymer and about 25 parts to about 60 parts by weight of an acrylonitrile polymer. Molecular mixture composition. 4. The chloroprene polymer is polychloroprene or (a) 2-
Chloro-1,3-butadiene and (b) 2,3-dichloro-1,3-butadiene;
The polymer composition according to claim 1, wherein the copolymer is a copolymer of monomers having at least one monomer selected from the group consisting of 2,3-dibromo-1,3-butadiene and 1,3-butadiene. object. 5. The polymer mixture composition according to claim 1, wherein the acrylonitrile copolymer is a copolymer of acrylonitrile and butadiene. 6. The polymer mixture composition according to claim 5, wherein the acrylonitrile copolymer is a copolymer of acrylonitrile and butadiene. 7. The chloroprene polymer is polychloroprene or (a) 2-
Chloro-1,3-butadiene and (b) 2,3-dichloro-1,3-butadiene;
Selected from the group consisting of 2,3-dibromo-1,3-butadiene, 2-chloro-3-bromo-1,3-butadiene, 2-bromo-3-chloro-1,3-butadiene and 1,3-butadiene A polymer blend composition according to claim 1, wherein the polymer mixture is a copolymer of monomers having at least one monomer added thereto, and the acrylonitrile copolymer is a carboxylated copolymer of acrylonitrile and butadiene. 8. A vulcanizate of the composition according to claim 1. 9. The sulfide according to claim 8, wherein the sulfide is in the form of a thin film. 10. The vulcanizate of claim 9, wherein said film is 0.05 to 50 mils thick. 11. The vulcanizate of claim 10, wherein said thin film is between 0.1 and 20 mils thick. 12. The thin film has a tensile strength of at least 9MPA and at least 30MPa.
11. The vulcanizate according to claim 10, having an elongation of 0%. 13. The vulcanizate of claim 12, wherein said thin film has a tensile strength of at least 12.5 MPa and an elongation of at least 500%. 14. (a) from about 10 parts by weight to about 10 parts by weight, based on 100 parts by weight of total polymer.
A pre-cured polymer mixture composition having 90 parts by weight of the chloroprene polymer and about 10 parts by weight to about 90 parts by weight of the nitrile polymer, having the polymer mixture composition cured of the composition; and b) Elastic weight with tensile strength greater than 9MPA and elongation greater than 300%
A molded elastic product consisting of coalesced layers. 15. The polymer mixture composition before curing comprises about 20 parts to about 85 parts by weight of a chloroprene polymer and about 15 parts to about 80 parts by weight of an acrylonitrile polymer. 15. The molded elastic product according to 14. 16. The molding of claim 14, wherein the composition comprises about 40 parts to about 75 parts by weight of a chloroprene polymer and about 25 parts to about 60 parts by weight of an acrylonitrile polymer. Molded elastic products. 17. The molded elastic product of claim 14, wherein said nitrile copolymer is an acrylonitrile-butadiene copolymer. 18. The method of claim 1, wherein the acrylonitrile-butadiene copolymer is a carboxylated acrylonitrile-butadiene copolymer.
8. The molded elastic product according to 7. 19. The molded resilient product of claim 14, wherein said tensile strength is greater than 12.5 MPa and said elongation is greater than 500%. 20. The layer of resilient material is essentially water and water vapor impervious, (d) can be stretched to ensure conformity to a human body part, and
Conforms to the shape of the body part, thereby permitting an initial pressurization on the human body part and allowing the human body part to relax to reduced pressure and stretch in one minute after being stretched 15. The molded resilient product of claim 14, wherein the molded product is relaxed to a value greater than 60% of the pressure and reaches a value greater than 50% of the initial pressure 10 minutes after stretching. 21. The molded resilient product of claim 20, wherein said layer has a thickness of about 0.05 to about 50 mils. 22. The molded resilient product of claim 20, wherein said layer has a thickness of about 0.1 to about 20 mils. 23. The molded resilient product of claim 20, wherein the product is a glove. 24. The molded resilient product of claim 20, wherein the product is a condom. 25. The molded resilient product of claim 20, wherein the product is a breathing bag.