Vulcanization composition for reducing allergenic potential and elastomeric articles formed therewith

Abstract

To provide latex dispersions, elastomeric articles formed using the latex dispersions, coating compositions for elastomeric articles, and methods for preparing a reduced-allergenicity polyisoprene elastomeric article.SOLUTION: A latex dispersion comprises: a rubber component including polyisoprene; and a vulcanization composition. The vulcanization composition comprises: a source of sulfur; at least one fugitive dihydrocarbyl xanthogen polysulfide accelerator; at least one aldehyde-aniline condensate; and a metal oxide. Preferably, the vulcanization composition is free of non-fugitive accelerators. The vulcanization composition comprises only one fugitive dihydrocarbyl xanthogen polysulfide accelerator and only one aldehyde-aniline condensate. Preferably, the composition is free of additional compounds that function as accelerators for vulcanizing elastomers.SELECTED DRAWING: None

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. patent application Ser. No. 16 / 216,640, filed Dec. 11, 2018. No. 6,313,523, filed on December 13, 2017, which claims priority to U.S. Provisional Patent Application No. The applications claim priority to US Pat. No. 62 / 598,048 and are entitled "Allergen Potential." Vulcanized composition for reducing shock and elastomeric article formed therewith (V ULCANIZATION COMPOSITION FOR REDUCING AL LERGENIC POTENTIAL AND ELASTOMERIC ARTIC The disclosure of each priority application is incorporated herein by reference. No. 6,399,433, which is incorporated herein in its entirety. [Background technology]

[0002] The present invention relates generally to vulcanizing compounds, and more particularly to vulcanizing compounds for vulcanizing elastomeric articles. The present invention relates to a method for producing a composition having high allergenic potential, including an enhancer composition for the production of a composition having high allergenic potential. The present invention relates to a vulcanized composition having reduced thermal conductivity.

[0003] Allergies associated with the use of elastomeric articles in the medical field include: (a) Type I immediate allergy; type IV hypersensitivity, IgE mediated allergy, and (b) type IV delayed allergy. There are two types of allergies: extended hypersensitivity and cell mediated allergy. do.

[0004] Type I hypersensitivity reactions are mediated by IgE immunoglobulin and their effects are immediate. Symptoms generally become apparent within minutes of exposure to the allergen and consist of localized urticaria, facial swelling, Symptoms include swelling, watery eyes, rhinitis, asthma, and in very rare cases, anaphylactic shock. The energy content has been linked to the residual extractable proteins present in natural rubber latex products. do.

[0005] Water leaching, chlorination, and low protein or deproteinization Measures to reduce extractable protein in latex gloves, such as the use of modified latex, have been implemented. However, there are many techniques available for treating rheumatoid arthritis, including those with allergies to natural rubber latex proteins. The use of synthetic gloves is recommended for healthcare workers and patients with The synthetic materials used are polyisoprene, acrylonitrile-butadiene (nitrile), polychlorinated Includes roloprene (neoprene), polyurethane, and polyvinyl chloride.

[0006] As a result of the incidence of type I reactions in response to contact with natural rubber proteins, particularly on the skin and In the manufacture of medical devices that come into contact with natural rubber latex, synthetic latex that does not contain natural rubber latex proteins is used. Considering cost and performance, synthetic cellulose is suitable for glove manufacturing. Latex includes nitrile latex and polyurethane latex for examination gloves, For surgical gloves, polychloroprene latex and polyisoprene latex are used. In surgical gloves, polyisoprene latex has properties similar to those of natural rubber, especially tensile strength. It is expensive, but generally used as a polychrome because it has extreme elongation, flexibility and a comfortable feel. It is preferred over propylene.

[0007] However, type IV allergic reactions can be induced by natural or synthetic elastomeric articles. Synthetic latex is called compounded latex. The use of certain chemicals that can be found in acetex (acetaminophen) can still cause allergic reactions. Type IV delayed hypersensitivity reactions are cell-mediated allergies to certain chemicals. Type IV allergic reaction. Symptoms first appear 48 to 96 hours after contact. Potential triggering chemicals include thiurams, mercaptobenzothiazoles, and dithiocarbamates. salts (dithiocarbamates), diphenylguanidine, and thiourea These include vulcanization accelerators, which are used in the process of preparing elastomeric articles. The U.S. Food and Drug Administration (FDA) has recommended that thiazoles, thiurams, and carbamides be restricted in rubber products. Carbamates can induce type IV allergic reactions in humans. “Guidance for Industry and FDA Reviewers / Staff: Premarket Notification [510(k)] Submissions for Testing for Skin Sensitization to Chemicals in Natural R ubber Products,” US Department of Heal th and Human Services(1999). Therefore, the completed The level of accelerators used is minimized so that residual accelerators in the polymeric article are very low. It is important to do so.

[0008] Elastomeric articles are commonly manufactured using a latex dipping process, which The molds or formers are then filled with a coagulant solution (usually calcium nitrate). After evaporating the solvent, the product is coated with a coagulant. The mold / tool ​​is placed on the compounded latex so that a film of coagulated rubber particles is deposited on it. After the latex film is gelled using heat, the wet gelled latex film is The rubber is leached in water and then dried and vulcanized in a hot air oven. is chemically crosslinked.

[0009] Most commonly, the crosslinking agent is sulfur. However, sulfur alone is ineffective in forming crosslinks. Traditionally, sulfur has always been used in combination with vulcanization accelerators and activators.

[0010] Vulcanization accelerators are usually organic compounds that increase the speed and efficiency of sulfur crosslinking, while An activator is a compound that increases the efficiency of the accelerator. Examples of accelerators used in ding include thiurams, dithiocarbamates, mercapto These include benzthiazole, diphenylguanidine and thiourea. After vulcanization, Depending on the amount of accelerator used, some or most of the accelerator may be chemically bound to the rubber matrix. However, some may remain unreacted and remain as a residue in the finished elastomeric article. do.

[0011] The vulcanization activators used in latex compounding are usually zinc oxide, magnesium oxide, Metal oxides such as lead.

[0012] Accelerator-induced crosslinking, including sulfur- and accelerator-free crosslinking Various methods have been attempted to minimize or eliminate type V allergic reactions. These include (a) cross-linking using gamma radiation, (b) cross-linking using organic peroxides, and (c) Crosslinking with zinc oxide alone via carboxyl-zinc ionic bonds, and (d) formation This involves the introduction of functional groups into the polymer backbone that can form crosslinks after the article is manufactured. All of these approaches have drawbacks. For example, (a) and (b) The approach results in products with lower physical properties and lower aging resistance than sulfur vulcanizates. vinegar.

[0013] Another approach is the use of safer enhancers. These reduce the potency of the allergen. For example, zinc dibenzyldithiocarbamate (Zinc dibenzyldithiocarbamate) is a lower ionizing accelerator. dibenzyl dithiocarbamate (ZBEC), diisononyl dithiocarbamate Zinc diisononyl dithiocarbamate e) Use high molecular weight accelerators with low allergenic potential, such as ZDNC. Due to their high molecular weight, these types of accelerators are suitable for use with natural rubber and synthetic polyisoprene. More compatible with rubber and therefore more soluble in the rubber matrix As a result, it blooms onto the rubber surface and can cause potential allergic reactions when it comes into contact with the user. For the same reason, very little of the high molecular weight accelerators that cause reactions are extracted from rubber. Very few high molecular weight accelerators are available. ZDNC is preferred over ZBEC, but This is because ZDNC has a higher solubility in natural rubber (approximately 3% wt / w), whereas ZBE The solubility of C is only about 0.5% w / w.

[0014] A further approach is to use transient accelerators, i.e. those that are completely used up during vulcanization and do not remain in the product. The key to success is to use a combination of promoters that leave no residue. Examples of such fugitive promoters are Examples of the polysulfide include diisopropyl xanthogen polysulfide (diisopropyl xanthogen polysulfide). Diisopropyl xanthogen polysulfide (DIXP) Disulfide, Diisopropylxanthogen Trisulfide, Diisopropylxanthogen Diisopropyl xanthogen tetrasulfide, diisopropyl xanthogen pentasulfide, diisoamylxanthate diisoamyl xanthogen trisulfide, diisoamyl xanthogen tetrasulfide, diisoamyl chi Xanthogen pentasulfide, diethylxanthogen tetrasulfide, dibutylxanthogen Dihydrocarbyl ketones including dibutyl xanthate tetrasulfide and dibutyl xanthate disulfide Xanthogen polysulfide (dihydrocarbyl xanthogen pol Dialkyl xanthogen polysulfides (dialkyl xa xanthogen polysulfides) [short form "xanthogen polysulfides" "Ruffido" is one example.

[0015] As a typical example, DIXP is heated to high temperatures alone, but it does not evaporate or dissolve. DIXP does not completely decompose into gaseous products. However, DIXP can be used in combination with diene-containing polymers or When used with sulfur and zinc oxide to crosslink rubber, it is completely consumed. The main reaction products are sulfur bridges, isopropanol, and carbon disulfide. Propanol and carbon disulfide are volatile at crosslinking / vulcanization temperatures and should not be applied to polymers or rubbers. DIXP does not contain nitrogen in its chemical structure, so it is It is also not possible to generate N-nitrosamines associated with dithiocarbamate accelerators. In addition, certain nitrosamines are believed to be carcinogenic, and their formation However, DIXP alone can have a significant effect on polyisoprene articles, especially in In the present invention, the sulfur crosslinking is promoted enough to produce a useful product. The resulting articles have too low tensile strength. Therefore, DIXP is always used in conjunction with other It is used in combination with an accelerator.

[0016] Various accelerator compositions have been disclosed in the prior art, some of which are discussed below. can be.

[0017] term

[0018] 1.0 phr of the ingredient is 100 parts dry weight of rubber. 1.0 part dry weight of the ingredient per 1.0 part dry weight rubber weight).

[0019] Abbreviation: DIXP - Diisopropyl xanthogen polysulfide n polysulfide), TMTD-Tetramethylthiuram disulfide disulfide), ZMBT - zinc mercaptobenzothiazo le), ZDBC-zinc dibutyl dithiocarbamate, ZDEC-zinc diethyl dithiocarbamate, DPG -Diphenyl guanidine, ZDNC-diisononyldithiocarba Zinc diisononyl dithiocarbamate, MBT-mercaptobenzothiazo mercaptobenzothiazole, SDBC-sodium dibutyldithiocarbamate (SOD ium dibutyl dithiocarbamate), SDEC-sodium diethyldithiocarbamate (s sodium diethyl dithiocarbamate, sodium SIX-isopropyl xanthate (s odium isopropyl xanthate, ZIX-zinc isopropyl xanthate yl xanthate).

[0020] Stevenson, U.S. Pat. No. 4,695,609, discloses a dihydrocarbyl xanthan Diphenyl polysulfides (1.5-4 phr DIXP) and metal hydrocarbyl xants Metal hydrocarbyl xanthate (0.05~5phr isopropyl / isobutyl Vulcanizable materials containing less than 0.4 phr of nitrosable materials US Pat. No. 5,999,333 discloses an accelerator system for use in curing rubber compositions which is suitable for use in curing rubber compositions which are ....

[0021] Stevenson, U.S. Pat. No. 5,254,635, discloses a dihydrocarbyl xanthan Dibenzyl thiuram sulfide (1-6 phr), dibenzyl thiuram sulfide (up to 1.5 phr) r), xanthate compounds (0-5 phr) and less than 0.2 phr A sulfur-free rubber vulcanizable composition containing a nitrosatizable material is disclosed.

[0022] Saks' U.S. Patent No. 6,618,861 covers 2 phr of TMTD, 0.2 phr of ZMBT, 0.2phr ZDBC, 0.2phr diphenylthiourea and 0.2p Polyisoprene compositions containing an accelerator system containing hr of ZDEC are disclosed.

[0023] Lucas et al., U.S. Patent Application Publication No. 2003 / 0161975, discloses a defect-free polyimide Tetrabenzyl thiuram disulfide or ZB is used to make Soprene condoms. The EC discloses the use of sulfur and DIXP. The band is made of conventional zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, etc. The accelerator composition has improved stability compared to latexes formed using the accelerators listed above. , 1.5 phr DIXP, 0.6 phr tetrabenzyl / tetraethyl thiuram di and sulfides.

[0024] Wang et al., U.S. Patents 6,828,387 and 8,273,810, disclose Polyisocyanate with an accelerator composition containing octacarbamate, thiazole, and guanidine Disclosed is a formulation for prene, in which the dry weight of each is from about 0.50 to about 1.00 phr. In Example 1, 0.50 phr of ZDEC and 0.50 phr of ZMBT are used. 1.00 phr of DPG.

[0025] The synergistic combination of DIXP and ZDNC has been shown to be effective in the synthesis of natural rubber latex and synthetic polyisocyanates. It is recommended as a safer accelerator for use with polypropylene latex. Kraborty et al., "New sustainable solutions for latex applications," Accelerators: An Update” International Latex Conference (2005)(“Novel Sustainable Accelerators for Latex Applications-Update,” International Latex Conference (2005)).

[0026] To vulcanize polychloroprene, conventional cure packages use sulfur, a non-fugitive accelerator. , and zinc oxide. Non-transient accelerators that may be used include dibutyldithiocarbamate. Zinc (ZDBC); Tetraethylthiuram disulfide and sodium dibutyldithiocarbamate A mixture of thorium; and diphenylthiourea (thiocarbanilide) and diphenylguanidine. Contains a mixture of gin (Carl, Neoprene Latex, chapter 3, published by EI, du Pont de Nemours& Co. (1962). However, residues of these non-transient enhancers in products may be IV It may induce type-II allergic reactions.

[0027] Chakraborty et al. (2nd International Rubber Glove Conference 2004, Kuala Lumpur, Ma Lesia(2nd International Rubber Glove Conference 2004, Kuala Lumpur, Malaysia )) is a combination of sulfur and two accelerators (ZDNC and DIXP, or ZDEC and M BT), zinc oxide, and two antioxidants (AO2246 and MMBI). Chakraborty et al. have reported a safer formulation for PI latex. The authors disclose a 0.4p accelerator system and a conventional accelerator system. hr of DIXP and 0.4 phr of ZDNC, while the latter system contains 0.5 phr of ZD EC and 0.5 phr of MBT. For DIXP / ZDNC compositions, The latex film was allowed to age for 8 days at 30°C before it gave good tensile strength properties. The test film must be prepared by casting the latex on a glass plate. The coating is prepared by mixing the cellulose acetate and the cellulose acetate solution in a 200-ml container and drying at ambient temperature before curing. This differs from the method used in commercial glove production by "gulant dipping."

[0028] Virdi et al. (8th International Rubber Gloves Conference and Exhibition 2016, Kuala Lumpur, Ma Lesia(8th International Rubber Glove Conference and Exihition 2016, Kuala Lu mpur, Malaysia) was presented by DIXP (0.5phr) and ZDN C (0.5 phr) with metal xanthate (0.3 SIX or 0.3 ZIX) In one embodiment, an accelerator composition for synthetic polyisoprene is disclosed, which comprises in combination: ASTM D3577 Standard Specification for Rubber Surgical Gloves (Type II Synthetic Latex Gloves) The resulting coagulant-dipped film has good tensile strength values ​​that can meet the standards. The tex is matured at 30°C or 35°C for 24 hours before being immersed in a coagulant to form a membrane. They are also metal xanthate free and contain 0.5 phr of DIXP and The accelerator composition containing 0.5 phr of ZDNC (described above by Chakraborty et al. The compositions shown produce coagulant-dipped films with very poor tensile strength properties. This finding indicates that the films formed by casting on glass plates This is quite different from the findings of Chakraborty et al., who found that it gives good tensile strength properties. It's different.

[0029] U.S. Patent No. 7,041,746 to Dzikowiczn discloses a dithiocarbamate ( 0.5-4.0 phr), thiourea (0.2-4.0 phr) and sometimes thiazo No. 5,333,393 discloses an accelerator system for synthetic polyisoprene containing 0.5 phr of methyl ethyl ketone.

[0030] Lucas et al., U.S. Patent No. 8,087,412, discloses a synthetic polyisoprene article (cond. Pre-vulcanization compositions and post-vulcanization compositions for gloves and A post vulcanization composition is disclosed, in which The accelerator system contains ZDEC / ZDBC (0.4~1.0phr), a post-vulcanization accelerator system. The stem is SDBC / SDEC (0.05-0.50 phr) and DIXP / Xanthophylline. Contains sulfide / thiuram (0.2~0.6 phr).

[0031] Van Jole, U.S. Pat. No. 8,673,172, discloses a method for the preparation of conjugated diene monomers, e.g. Polyisoprene and conjugated diene monomers with vinyl aromatic comonomers 2. A latex accelerator formulation for a synthetic rubber latex derived from DIXP, The present invention discloses an accelerator composition containing an alkyldithiocarbamate and DPG. wherein each of the accelerator compositions is present in a concentration of 0.25 to 1.00 phr.

[0032] Chen et al., U.S. Pat. No. 8,980,391, discloses a method for producing a ferroelectric material comprising the steps of: Vulcanizing compositions containing a fugitive accelerator (DIXP) that leaves no detectable residual DIXP in the article Polychloroprene, which has low allergenic potential, is produced by using The article discloses a surgical glove that meets the ASTM D3577 standard. This is due to the sulfur crosslinks and reactive tertiary allylic chlorine atoms on the polymer chains. (reactive tertiary allylic chlorine atom Cross-linking between polymer chains promoted by s) can be achieved using zinc oxide as a catalyst. See Carl, Neoprene Latex, chapter 3.

[0033] U.S. Patent Application Publication No. 2015 / 0128329 to Amarasekera et al. Isoprene polymers and thiourea, benzothiazole sulfenamide, thiazole or a first accelerator comprising a thiuram or dithiocarbamate, or a combination thereof; and a second accelerator comprising a xanthogen polysulfide or a combination thereof. A glove comprising a latex composition is disclosed. Three examples are given (Examples 1-3). In the non-transient accelerator (thiourea, benzothiazole sulfenamide / thiazole , dithiocarbamates, and thiurams) was 1.4-1.5 phr. , the xanthogen polysulfide level was 0.3 phr.

[0034] Krutzer, U.S. Patent Application Publication No. 2016 / 0108154, discloses a method for the preparation of a sulfur donor ( Thiuram as an accelerator and sulfur donor 0.5-10 phr and combination of thiocarbamate or dithiocarbamate 0.05 For use with synthetic isoprene polymers, including polyisoprene, containing up to 2.0 phr. The document discloses an accelerator system for

[0035] Aldehyde amines are reaction products of various aldehydes and amines, and were first discovered in 1910. It is known to be used as a dry rubber accelerator in the mid-single. The amine accelerators are aldehyde-aniline, butyraldehyde-aniline and heptaldehyde-aniline. The most widely used aldehyde-amine accelerators are aldehyde-aniline (HA). Currently, the use of aldehyde-amine accelerators is limited. These accelerators can be used with hard rubbers such as ebonite. If used, the accelerator 2.5 phr can be used with 30-50 phr of sulfur. Used as a secondary accelerator at 0.20-0.30 phr with phenyl or sulfenamide accelerators. It is commonly used for rubber compounding. s,Materials,and Techniques.Second Editio n, by Fred W. Barlow p110, Marcel Dekker, I Inc., New York, 1993). The accelerator used in drying rubber is latex. It can be used on rubber, but the effectiveness and efficiency may not be the same. is not known to be used in the manufacture of rubber gloves. Dry rubber and latex are cured. The use of "xanthogen polysulfides" in combination with other accelerators to achieve the desired reaction is evenson (U.S. Patent No. 4,695,609; U.S. Patent No. 5,254,635) The combination of aldehyde-aniline with DIXP has not been considered so far. Not yet. Summary of the Invention [Problem to be solved by the invention]

[0036] Therefore, it is a simpler method used to vulcanize elastomeric articles with small amounts of accelerators. A vulcanized composition having reduced allergen potential, particularly for polyisoprene applications. There is a need for a vulcanization composition for the vulcanization of 1,2-dichlorophenyl ether (1,2-dichlorophenyl ether) and 1,2-dichlorophenyl ether (1,2-dichlorophenyl ether). In combination, dithiocarbamates, thiazoles, thiurams, guanidines and thioureas The present invention combines low levels of additional accelerators without traditional accelerators such as chlorine. The present invention also provides a vulcanizable composition comprising an aldehyde-aniline as an additional accelerator effective in the vulcanization of the vulcanization composition. The present invention also relates to polyisoprene-based elastomeric articles formed using the Producing a vulcanized composition with reduced allergenicity and a method of using the vulcanizing composition to vulcanize an elastomeric article. . [Means for solving the problem]

[0037] Summary of the Invention Certain aspects of the present disclosure include an accelerator composition used to vulcanize elastomeric articles. The vulcanizable composition contains higher levels of non-fugitive and fugitive accelerators. The allergen potential is reduced compared to vulcanized compositions having the composition. and an elastomeric article formed using a vulcanized composition having a higher level of the accelerator composition. In comparison, it can be used to form elastomeric articles that have reduced allergen potential. The present invention further provides a method for producing a vulcanized composition having reduced allergenicity. The present invention relates to a method for vulcanizing an elastomeric article, and to a method for using the vulcanizing composition to vulcanize an elastomeric article.

[0038] The present invention relates to vulcanizable compositions, latex dispersions, and elastomers formed using conventional techniques. Vulcanized compositions having reduced or eliminated allergen potential compared to stomer articles The present invention provides a method for producing a elastomeric polymeric material comprising the steps of: According to some aspects, the present invention provides This results in the reduction or elimination of Type I and Type IV allergenicity. Compositions, latex dispersions, elastomeric articles, and methods for elastomeric articles This is especially helpful for healthcare providers and those who are looking to avoid problems related to allergic reactions. Both patients and their families are frequently and / or over long periods of time exposed to these potential allergen sources. This is beneficial in the medical field where exposure is high.

[0039] According to one aspect of the invention, the present invention provides a fugitive xanthogen polysulfide accelerator and The present invention relates to a vulcanizable composition comprising an aldehyde-aniline accelerator combination. According to the present invention, a single fugitive xanthogen polysulfide accelerator and a single arsenic For vulcanized compositions containing a dehyde-aniline accelerator, the vulcanized composition does not contain an additional accelerator. According to another aspect of the present invention, the present invention provides a polysulfide derivative comprising diisopropyl xanthogen and and a vulcanization composition containing a heptaldehyde-aniline condensate as an accelerator. According to one embodiment, the vulcanization composition is a vulcanization composition comprising a non-transient accelerator and a higher level of accelerator. It exhibits reduced allergenicity compared to sulfur compositions.

[0040] According to a further embodiment, the elastomer is polyisoprene. The polyisoprene may be natural rubber polyisoprene or synthetic polyisoprene. The latex formulation is used to make gloves (specifically medical gloves, more specifically examination and and surgical gloves), as well as condoms, probe covers, dental dams, finger cots, and The elastomeric material may be used to form elastomeric articles, which may include, but are not limited to, catheters.

[0041] Any features, structures, or steps disclosed herein may be combined with any other features, structures, or steps disclosed herein. Can be replaced with, combined with, or eliminate a feature, structure, or step Additionally, for purposes of summarizing this disclosure, the term "devices" may be used interchangeably. Certain aspects, advantages, and features of the present invention are described herein. or all of the above may be achieved in accordance with any particular embodiment disclosed herein. It should be understood that no individual aspect of this disclosure is essential or required. stomach. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0042] Detailed Description The detailed description set forth below is intended as an illustration of the various configurations and features described herein. The detailed description includes various concepts and is not intended to represent the only configurations in which the concepts may be practiced. It contains specific details to fully understand the concepts. However, these concepts are It will be apparent to one skilled in the art that the present invention may be practiced without these specific details.

[0043] The present invention generally comprises an accelerator composition used to vulcanize elastomeric articles. Regarding the vulcanization composition, the accelerator composition is used in the vulcanization composition having a higher accelerator composition. and (b) having reduced allergenic potential compared to elastomeric articles formed from The vulcanization composition includes a temporary vulcanization accelerator and an additional accelerator. The amount of the additional accelerator is The amount is significantly less than that in conventional compositions. The present invention also provides a composition formed using the vulcanized composition. The present invention further relates to a latex dispersion and an elastomeric article having reduced adhesion. Method for preparing an allergenic vulcanizable composition and a vulcanizable composition for vulcanizing an elastomeric article - Patents.com The present invention relates to methods of using the compositions.

[0044] The temporary vulcanization accelerators for use in accordance with the present invention include xanthogen polysulfides. Diisopropyl xanthogen polysulfide (DIXP), diisopropyl xanthate Gen Disulfide, Diisopropyl Xanthate Trisulfide, Diisopropyl Xanthate xanthogen tetrasulfide, diisopropyl xanthogen pentasulfide, diisoamyl Xanthogen trisulfide, diisoamyl xanthogen tetrasulfide, diisoamyl Xanthogen pentasulfide, diethylxanthogen tetrasulfide, dibutyl xanthogen Xanthogen tetrasulfide and dibutyl xanthogen disulfide are preferred according to the present invention. These are preferred fugitive xanthogen polysulfides that may be developed in the future. Additional fugitive xanthogen polysulfides may also be used in the accelerator compositions, latex dispersions, and the like of the present invention. It is expected that the vulcanizable compositions of the present invention will find use in the manufacture of elastomeric and non-elastomeric articles, as well as in the manufacture of composites and elastomeric articles. In the accelerator composition of the present invention, fugitive xanthogen polysulfides are useful. are consumed during vulcanization by binding to the rubber matrix and are not available for vulcanization. The formation of gases and / or volatile liquids as by-products that evaporate at the high temperatures applied. This is because it does not leave any residue on the elastomeric article. In the case of diphenylsulfide (DIXP), the compound produces isopropyl alcohol as a by-product. Forms carbon disulfide gas.

[0045] Additional accelerator compositions that may be utilized in the present invention include aldehyde-anilines. The accelerators include heptaldehyde-aniline (HA) and butyraldehyde-aniline (B A) is preferred, but other aldehyde-anilines may also be used. Hydaniline is a condensation product. In a preferred embodiment, heptaldehyde-aniline (H A) is an additional promoter.

[0046] The present invention also provides a method for producing a rubber composition comprising the steps of: (a) forming a rubber-based polymeric polymeric polymeric polymer having a polyisoprene rubber and an aldehyde-aniline as an additional accelerator; Elastomeric articles vulcanized with phosphorus and xanthogen polysulfide accelerators According to some embodiments, the elastomeric article is a glove (particularly a medical glove). , more specifically examination and surgical gloves), as well as condoms, probe covers, teeth In some embodiments, such facilitation may include surgical dams, finger cots, and catheters. Polyisoprene surgical and examination gloves made with the agent composition are provided.

[0047] Elastomeric articles made with large amounts of accelerator compositions, especially non-fugitive accelerators, have Contains residual accelerators that can cause Type IV allergic reactions in The produced elastomeric articles are characterized by the presence of extractables associated with Type I allergic reactions in humans. The elastomeric article, accelerator composition, latex and the like according to the present invention contain latex proteins. The method of making the accelerator composition and the method of vulcanizing the elastomeric article are It does not ingest any sebum and contains high levels of residual promoters, so it is not susceptible to type I allergies. The likelihood of reactions and type IV allergic reactions is reduced or eliminated.

[0048] Non-transient enhancer compositions are known to induce Type IV allergic reactions in humans. These include thiazoles, thiurams, dithiocarbamates, guanidines, and thioureas. It can be seen.

[0049] The compositions and methods of the present invention are described in more detail below.

[0050] Vulcanized Composition

[0051] The vulcanizable composition of the present invention preferably comprises a sulfur source, an accelerator composition, and an activator. The accelerator composition may include a temporary accelerator and an additional accelerator. Allergens of the Vulcanizing Composition According to one embodiment of the present invention, the effect of the elemental sulfur is minimized or eliminated. l sulfur), a single xanthogen polysulfide transient accelerator, zinc oxide, and In rubber terminology, the term "single component" refers to the combination of a single aldehyde-aniline accelerator with a single aldehyde-aniline accelerator. "phr" stands for hundred parts (dry weight) of rubber. Parts (dry weight) of that ingredient per eight t)) Additional accelerator (aldehyde-aniline condensate) is about 0.05 phr to about 0.50 phr, preferably about 0.075 phr to about 0.35 phr, more preferably The range is about 0.10 phr to about 0.25 phr. Transient accelerators (xanthogen poly sulfide) is about 0.50 phr to about 5.0 phr, preferably about 0.75 phr to about 3.0 phr, more preferably in the range of about 1.0 phr to about 2.5 phr. Materials include natural rubber, polyurethane, polybutadiene, polychloroprene (neoprene), tolyl rubber, block copolymers of styrene and butadiene, styrene and isoprene block copolymers of ethylenediaminetetraacetate, polyisoprene, and the like of the above polymers or elastomers. It can be used to vulcanize elastomers, including combinations or mixtures. In certain preferred embodiments, the elastomer is polyisoprene. may be natural or synthetic.

[0052] In some embodiments of the present invention, allergenicity of the vulcanized composition is minimized or eliminated altogether. In some embodiments, the sulfur source used in the vulcanized composition comprises elemental sulfur. For example, only elemental sulfur is used. The elemental sulfur is present in an amount of about 0.5 to about 3 phr, preferably about 1 to 2 phr. phr, more preferably in the range of 1 to about 1.5 phr.

[0053] Vulcanization activators include zinc oxide, magnesium oxide, lead oxide, and combinations thereof. Zinc oxide can be used in certain embodiments of the present invention as a vulcanizing agent. The activator is used in an amount of about 0.1 to about 2.0 phr, preferably about 0.1 to about 2.0 phr. It is about 1.0 phr, and more preferably in the range of about 0.2 to about 0.8 phr.

[0054] In some embodiments of the present invention, the allergenicity of the vulcanized composition is minimized or eliminated altogether. In some embodiments, one vulcanization accelerator used in accordance with the present invention is a fugitive xanthate. According to some embodiments, the transient xanthogen polysulfides are A sulfide has two or more sulfide groups, i.e., three sulfide groups (trisulfide), Four sulfide groups (tetrasulfide), five sulfide groups (pentasulfide), etc. According to a further aspect of the present invention, a fugitive xanthogen is a polysulfide. The polysulfide is dihydrocarbyl xanthogen polysulfide (diisopropyl xanthate). Diisopropyl xanthogen polysulfide (DIXP), diisopropyl xanthogen disulfide, diisopropyl xanthogen disulfide Diisopropyl xanthogen trisulfide, diisopropyl xanthogen tetrasulfide , diisopropyl xanthogen pentasulfide, diisoamyl xanthogen trisulfide diisoamylxanthogen tetrasulfide, diisoamylxanthogen pentasulfide Sulfide, diethyl xanthogen tetrasulfide, dibutyl xanthogen tetrasulfide These transient xanthogens include It should be noted that the polysulfide accelerator may also function as a sulfur donor. In one embodiment, the sulfur donor has low allergenic potential.

[0055] Additional accelerator compositions utilized in the present invention may include aldehyde amines. More specifically, these aldehyde amines can be aldehyde anilines. Typically, the additional accelerator is an aldehyde-aniline condensate. Accelerators of the present invention include: Heptaldehyde-aniline (HA) condensation product and butyraldehyde-aniline (BA) Condensations are included, but other aldehyde-aniline derivatives may also be used. In, heptaldehyde-aniline (HA) is an additional accelerator.

[0056] In one embodiment of the present invention, only a single fugitive xanthogen polysulfide accelerator is used. In the accelerator composition, only a single aldehyde aniline accelerator is used and no additional accelerator is used. Additional vulcanization accelerators are also excluded from the accelerator composition.

[0057] According to a further aspect of the present invention, DIXP and HA are the only vulcanization accelerators, Only the above is a compound that functions as a vulcanization accelerator contained in the vulcanization accelerator composition. Allergens When accelerator compositions having reduced or eliminated toxicity are prepared in accordance with the present invention, they advantageously include The additional compound, which may also function as a vulcanization accelerator, may include only DIXP and HA. In another embodiment, an additional transient accelerator is included in the accelerator composition. In any embodiment, these may include, but are not limited to, additional non-transient enhancers. The exclusion of is beneficial, but it is not without its drawbacks, such as the presence of additional vulcanization accelerators or the presence of additional non-transient accelerators. The use of the vulcanized composition is advantageous in that allergic reactions, particularly type IV allergic reactions, are prevented by the use of elastomers formed from the vulcanized composition. This is to increase the likelihood of this occurring to users of Tomer products.

[0058] Latex dispersions and elastomeric articles

[0059] The vulcanizable composition of the present invention can be used to prepare a latex dispersion. Tex dispersions are made of natural rubber, polyurethane, polybutadiene, polychloroprene (neo styrene, butadiene, nitrile rubber, block copolymers of styrene and butadiene, and isoprene block copolymers, polyisoprene, and the above polymers or ethylenediamines. The elastomer may be selected from a combination or mixture of elastomers. According to the present invention, a particularly preferred elastomer for use in the latex dispersion is poly(ethylene glycol). These latex dispersions are used in elastomer and vulcanization compositions as well as The composition may contain one or more different non-curing ingredients, such as antioxidants, stabilizers, etc. These include, but are not limited to, stabilizers, plasticizers, anti-ozonants, pigments, and fillers. According to one embodiment of the present invention, when manufacturing elastomeric articles (see, for example, U.S. Pat. No. 8,110,232), 66 or U.S. Pat. No. 6,828,387, both of which (which is incorporated herein by reference in its entirety), and the total solids content of the latex dispersion is The range is about 25% to about 49%.

[0060] The latex dispersion of the present invention containing the elastomer and vulcanizable composition is preferably used in the manufacture of gloves, specifically The present invention relates to preparing elastomeric articles, such as medical gloves, more specifically examination and surgical gloves. However, those skilled in the art will appreciate that the present disclosure may be used in methods for Use the guidance provided in the manual to ensure that condoms, probe covers, dental dams, and finger caps are Other elastomeric articles other than gloves, including but not limited to gloves, catheters, etc. It is believed that it can be prepared.

[0061] The elastomer of the present invention formed using the vulcanization composition and / or latex dispersion described above. The tomer articles can be manufactured using conventional manufacturing methods, such as coagulant dipping. In the "anode" coagulant dipping process, the coagulant-coated former is immersed in the dispersion. The "Teague" coagulant-dipped process is then allowed to harden to form the finished product. The process involves dipping a former into the dispersion, then into a coagulant, which then hardens to produce the finished product. These methods form a dispersion containing an elastomer by which a finished article is formed. Preferred elastomers include natural rubber, polyurethane, polybutadiene, and the like. Polychloroprene (neoprene), nitrile rubber, styrene and butadiene blocks copolymers, block copolymers of styrene and isoprene, and polyisoprene. According to a particular embodiment, a particularly preferred elastomer is polyisoprene. According to another embodiment, a vulcanizing composition comprising sulfur, zinc oxide, HA and DIXP is used. A vulcanized polyisoprene elastomeric article is provided.

[0062] HA has not been used in rubber gloves before. This invention is a rubber glove before aging. 24MPa (minimum) and ASTM 3577-09 standard requirements for surgical gloves (natural rubber) ASTM D 18 MPa after aging and before aging for synthetic rubber surgical gloves 3577-09 standard requirement of 17MPa (min) and 12MPa (min) after aging In order to obtain an elastomeric article having a tensile strength satisfying Polyisoprene latex can be vulcanized using a vulcanization composition comprising DIXP. We unexpectedly discovered that DIXP is a transient xanthogen polysulfide. Since no DIXP residue remains in the vulcanized gloves and the amount of HA required is small, this vulcanizate is used. Gloves manufactured with this material exhibit low allergenic potential.

[0063] The elastomeric articles of the present invention can be used in forming elastomeric articles. The latex dispersion may be formed using any of the additive components, which may include: The cured and uncured components described below have the same, similar or different chemical structure as the elastomer. The total additives used may include at least one of the following: The amount is about 0.5-49% by weight of the total dispersed phase solids.

[0064] When cured with sulfur, the primary curative is preferably elemental sulfur and / or aryl sulfur. According to one embodiment of the present invention, the present invention further comprises a sulfur donor having low or no sulfur potential. For example, only elemental sulfur is used.

[0065] Activators include zinc oxide, magnesium oxide and lead oxide. Not limited thereto. Zinc oxide is the most commonly used vulcanization activator. In one embodiment, Zinc oxide is used as the activator.

[0066] The vulcanization accelerator according to the present invention is a fugitive xanthogen polysulfide and an aldehyde-aldehyde. According to a further aspect of the invention, the fugitive xanthogen polysulfide is Diisopropyl xanthogen polysulfide (DIXP). Other xanthogen polysulfides Sulfide or dihydrocarbyl xanthogen Polysulfide (dialkyl xanthogen (including diisopropyl xanthogen disulfide, diisopropyl xanthogen disulfide, Luxanthogen trisulfide, diisopropyl xanthogen tetrasulfide, diiso Propyl xanthogen pentasulfide, diisoamyl xanthogen trisulfide, di Isoamylxanthogen tetrasulfide, diisoamylxanthogen pentasulfide , diethyl xanthogen tetrasulfide, dibutyl xanthogen tetrasulfide, di In one embodiment, the aldehyde-aniline is It's HA.

[0067] In the present invention, an elastomer dispersion formulation Any non-compounding formulations traditionally used in Hardening components can be used. For example, non-hardening components include antioxidants, stabilizers, These include, but are not limited to, plasticizers, anti-ozonants, pigments and fillers.

[0068] Suitable antioxidants that can be added to the elastomer dispersion include, but are not limited to: However, butylated hydroxytoluene (2,6-di-t-butyl-4-methylphenol) thiodiethylene bis-di-t-butyl-4-hydroxyphenylpropionate Butyration of hindered phenols such as butyl ester, p-cresol, and dicyclopentadiene Reaction products of hindered polyphenols, such as trimethyl-tris(di-t-butyl-4 -Hydroxybenzim)-benzene or octadecyldi-t-butyl-4-hydroxy Hindered phenols / polyphenols such as phenylpropionate, 6P Blends of PD with methylstyrene and bis-α-dimethylbenzyldiphenylamine amines such as mercaptothalamus imidazole zinc / phenol mixtures such as triazine Triazinone derivatives such as non-phenolic mixtures, poly(m-anisidine) Phenol antioxidant hydrazides such as aromatic amines, phenol with anhydride copolymers , 2,2'-methylene-bis-(4-methyl-6-t-butylphenol) and other phenols 2,4-dimethyl-6-(1-methylcyclohexyl)-p-cresol resoles, and styrenated phenols. One particularly preferred antioxidant is It is a butylated reaction product of p-cresol and dicyclopentadiene (e.g., Wi ngstay L).

[0069] In addition, colloid stabilizers such as pH adjusting alkali, surfactants, sodium caseinate, etc. An alkaline caseinate may be added to the aqueous phase.

[0070] Suitable plasticizers that can be added to the elastomer dispersion include fatty salts, mineral oils and and ester plasticizers.

[0071] According to some embodiments, the elastomeric material used to manufacture the elastomeric articles of the present invention An antiozonant is added to the ozone dispersion. Ozone is highly oxidizing agent, such as polyisoprene. Some elastomeric articles, such as those formed from polymers that are saturated, may be subjected to vigorous When included in the aqueous elastomer dispersion of the present invention, waxes, EPDM and Certain high molecular weight polymers, such as hydrogenated polydienes, provide such articles with excellent ozone resistance. Waxes form a physical barrier on the surface of rubber that protects against ozone. The waxes are linear paraffin wax and branched microcrystalline wax. There are two types of wax: Ozone resistant wax is blended with paraffin for maximum protection over a wide range of exposure temperatures. It is a mixture of microcrystalline waxes. Paraffin wax has about 20 to 50 particles. A suitable paraffin wax is a straight chain hydrocarbon molecule containing about 50 to 70 carbon atoms. 5°C, preferably 52 to 68°C. Microcrystalline waxes are non- Also known as crystalline wax, it is a hydrocarbon like paraffin wax, but it does not contain carbon. The chains are branched and have a higher molecular weight of about 40 to 70 carbon atoms per chain. Other examples of antiozonants that can be used in the present invention include N-1,3-dimethylbutyl -N'-Phenyl-p-phenylenediamine 6PPD and other alkyl / aryl p-phenyl Smectite containing phenylenediamine and alkyl-aryl-p-phenylenediamine Organoclay antiozonant complexes such as clays, N,N-disubstituted para-phenylenediamines, etc. Functionalized benzotriazole, tris(N-1,4-dimethylpentyl-p-phenylene) Diamino) 1,3,5 triazine and tris(N-alkyl-p-phenylenediamino) ) Triazines such as 1,3,5 triazine, and N-isopropyl-N'-phenyl- p-phenylenediamine (IPPD) and other p-phenylenediamines are included. In addition, paraffin wax (MW=300-500), micro Crystalline wax (MW=600~700) (along with paraffin wax) and low Polymers and macromolecules containing wax such as MW PE wax (MW=100~1100) Polymeric anti-ozonants such as diphenyldiamine, as well as EPDM and brominated isobutylene / Ozone-inactive polymers such as para-methylstyrene copolymer (BIMSM) are used as ozone inhibitors. It is preferable to use wax. One particularly preferred The wax is Michem Lube 180. The preferred wax dispersion is Antilux 600. .

[0072] Suitable pigments that may be added to the aqueous elastomer dispersion include titanium dioxide and iron oxide. These may include a wide range of natural and synthetic pigments.

[0073] Suitable fillers that can be added to the aqueous elastomer dispersion include clays, carbonates, Inorganic fillers such as calcium, talc, and silica, as well as crosslinked polymethylmethacrylate rates, finely divided urethane resin particles, and polyethylene microspheres. These include, but are not limited to, organic fillers.

[0074] Additional polymers may also be incorporated into the latex dispersions and elastomeric articles of the present invention. This can provide additional functionality or enhance the latex dispersion and elastomers. These functions / properties may include improved Improved damp / wet donning, improved liquid repellency These may include, but are not limited to, improved microbial resistance, improved resistance to degradation, etc. According to some aspects of the present invention, the additional polymer is selected from the group consisting of natural rubber, poly Urethane, polybutadiene, polychloroprene (neoprene), nitrile rubber, styrene and block copolymers of butadiene, block copolymers of styrene and isoprene. and polyisoprene.

[0075] In accordance with some aspects of the present invention, an elastomeric article is provided that includes a plurality of elastomeric layers. The multiple elastomeric layers can have the same or different compositions. Polychloroprene is a synthetic polyisoprene blended with polychloroprene. Applied to propylene elastomer articles to impart improved wet / wet wear properties to the articles. Another example can be a copolymer comprising nitrile mixed with polychloroprene. The coating composition is applied to a polychloroprene elastomer article to provide improved wetting of the article. In another example, it can be mixed with polyisoprene to provide wet wear properties. applying a coating composition containing the nitrile to a polyisoprene elastomer article, It can provide the article with improved wet / wet wear characteristics. A coating composition containing polyisoprene blended with a triacrylate was prepared by the method of the present invention. Applied to elastomeric articles to provide the articles with improved wet / wet wear properties In one example, the elastomeric article may include multiple layers of polyisoprene. do.

[0076] According to a further aspect of the invention, the elastomeric article is a powder or dendrimer. It can be formulated with or without flour. Flour and starch are commonly used. It is a donning agent that may be associated with allergic reactions. Thus, another aspect of the present invention relates to flour- and starch-free elastomeric articles. A further embodiment contains less than 5 mg of flour or starch, preferably less than 3 mg of flour or starch. is starch, more preferably less than 2 mg of flour or starch, most preferably less than 1 mg of powder or starch, substantially powder-free or starch-free These articles are made of the vulcanized elastomeric material described above. The composition is prepared using:

[0077] These and other aspects of the present invention are further illustrated in the non-limiting examples described below. Explained.

[0078] Preparing the gloves

[0079] Synthetic or natural rubber polyisoprene gloves are immersed in a standard coagulant. The base compound formula in Table 1 ion) was added to the accelerator composition for synthetic polyisoprene (Table 2) or natural rubber polyisoprene. It was prepared in combination with the accelerator composition for prene (Table 3).

[0080] The following preparations can be used (see Patent Nos. 8110266 and 68 (The entire specification of US Pat. No. 28387 is incorporated herein by reference), but any standard immersion process may be applied. be.

[0081] The vulcanization composition is a synthetic polyisoprene latex, a colloidal stabilizer (potassium ricinoleate), (potassium hydroxide, which also acts as a pH adjuster), crosslinker (sulfur), activator (zinc oxide ) and antioxidant (Winstay L) - (Table 1 base compound), and D Accelerator compositions containing IXP and heptaldehyde-aniline (Tables 2 and 3) To prepare the latex composition, various ingredients are mixed with the polyisoprene latex. The various ingredients are mixed with the latex as is customary in the latex art. The water-soluble component is dissolved in water to form an aqueous solution or dispersion. The water-insoluble solid components and the water-insoluble liquid components are dispersed in water to form an aqueous solution. After all ingredients are added, add water to mix the compounded latex to about 35 % total solids, and the pH of the latex is adjusted to approximately 11 for synthetic polyisoprene and approximately 12 for natural For natural rubber polyisoprene adjust to about 10.

[0082] The fully compounded latex is stirred and ready for dipping. Allow to age at ambient temperature of about 28°C to 32°C until fully combined.

[0083] Preparation of Powder-Free Gloves

[0084] Coagulation using ceramic molds (or formers) for evaluation of different latex compositions The gloves are prepared by dipping into the agent.

[0085] Preheat a clean ceramic mold in a hot air oven to 55-58°C. Calcium (as a release agent, about 4.0-5.0%) and Surfynol TG (as a wetting agent, about 0.15%) in a calcium nitrate coagulant solution (55-58°C, specific gravity approximately 1.130) The mold coated with the coagulant is dried in an oven (at 60°C for about 10 minutes) and then When the total solids content of the latex composition is 33.5%, The residence time in the tex is approximately 15 seconds, which results in a dry film thickness of approximately 0.20 mm. (To achieve this film thickness, the residence time and total solids content of the latex were varied. The latex film on the mold is suspended in the air for about 5 minutes to allow the latex film to dry. The latex film is then allowed to form a good gel. The sample is immersed in 100°C water for 5 minutes to extract water-soluble substances such as calcium nitrate and surfactants. The film on the mold is hung vertically at ambient temperature and allowed to dry for approximately 5 minutes. The film is then placed in an oven to dry and cure at 135°C for 30 minutes. The temperature and time may be adjusted to obtain the desired properties. After vulcanization, the gloves are allowed to cool to about ambient temperature. After cooling and lightly applying the modified starch to the film, the glove is removed from the former and turned inside out. The powdered gloves are called molded gloves.

[0086] Chlorination

[0087] To produce powder-free gloves, the gloves are post-treated by chlorination. Understand.

[0088] Turn the glove inside out so that the surface that did not come into contact with the mold during dipping is again on the outside of the glove. Chlorination reduces the amount of available chlorine to approximately 300 ppm (using a range of 200 to 700 ppm). Pre-washing of gloves with water prior to chlorination in an aqueous chlorine solution containing Then, neutralize the excess chlorine with sodium hydroxide solution, and then rinse with water (this step The chlorine level is measured on both surfaces of the final glove. The surface can be adjusted to provide desired properties such as reduced friction and adhesion. The glove is allowed to partially dry and then turned inside out again by hand and allowed to dry further.

[0089] Lubrication

[0090] For a good fit with wet or damp hands, rinse the wet gloves before drying them. The oil is then transferred to a tumbling washer for further lubrication process followed by a chlorination step. This lubrication process uses approximately 1.0% cetylpyridinium chloride, 1.0% silicone emulsion. The gloves were then washed with an aqueous solution containing 1.5% ammonium salt of alkyl phosphate. The levels of these three components determine the desired consistency of the finished glove. The gloves are removed from the tumbler and washed. Dry the gloves thoroughly and turn them inside out by hand. Then dry the gloves further. Easy to apply with dry or damp hands.

[0091] (For the chlorination and lubrication process, see U.S. Pat. No. 7,566,333, which is incorporated by reference.) (See No. 6,502.) EXAMPLES

[0092] The examples given below are for either natural rubber or synthetic polyisoprene. The base compound used for both is the same and is shown in Table 1 below. [Table 1]

[0093] Vulcanization composition for synthetic polyisoprene

[0094] Examples 1 to 10 are for synthetic polyisoprene, and the composition of the blend is: The base compound shown in Table 1 and the accelerator composition shown in Table 2 (expressed in phr) In Examples 1-8, the accelerator compositions (Table 2) contain various levels of DIXP (0.5 0-5.00 phr) combined with various levels of heptaldehyde-aniline (H A) (0.05-0.50 phr). Examples 9 and 10 contain DIXP or HA. The gloves are formed using a standard coagulant-dip process and vulcanized using hot air. The glove properties are shown in Table 4.

[0095] [Table 2]

[0096] Vulcanization composition for natural rubber polyisoprene

[0097] For Examples 11 to 16 of natural rubber polyisoprene, the composition of the compound to be blended is as shown in Table 1. The gloves contained the base compound shown in Table 1 and the accelerator composition shown in Table 3. The glove was formed using a binder dipping process and vulcanized using hot air. The glove properties are shown in Table 5. [Table 3]

[0098] Physical Properties of Polyisoprene Gloves

[0099] Tensile strength

[0100] Tensile strength is measured in accordance with ASTM D412 "Standard Test Methods for Vulcanized Rubber and Thermoplastic Elastomers" -Tensile (Standard Test Methods for Vulcanized Rubber and ThermoplasticElastomers-Tens The ASTM standard for surgical gloves is ASTM D3577- 09, Standard Specification for Rubber Surgical Gloves. The standard specifies that natural rubber latex is Type 1, and synthetic rubber latex is Type 2.

[0101] Physical properties of synthetic polyisoprene gloves.

[0102] Synthetic rubber as described in "ASTM D3577-09 Standard Specification for Rubber Surgical Gloves" The standard for tensile strength of surgical gloves is 17MPa or more before aging, and 17MPa or more after accelerated aging. After accelerated aging, the compressive strength is 12 MPa or more. [Table 4]

[0103] Molded gloves and chlorinated with latex maturation for 1-7 days The tensile properties of the gloves (both unaged and aged) are shown in Table 4. In eight accelerator compositions containing both P and HA, the aging time was 2 to 7 days, and the acetaldehyde ASTM D3577 Tensile Test of Aged and Unaged Synthetic Rubber Surgical Gloves Molded (i.e., powdered) and chlorinated (i.e., Powder-free gloves were obtained.

[0104] Unaged means "initial or current stage" ent stage), or "unaged" or "aged Aged can be defined as "after aging". ASTM D3577 Standard - Section 8.5: Physical Requirements Testing All surgical gloves meet the physical requirements (before and after accelerated aging) specified in Table #3. Accelerated aging tests shall be performed in accordance with Test Method D573. Aging conditions are 166 hours + / - 2 hours exposure to 70C + / - 2C; After exposure to temperatures of 0C+ / -2C for 22 hours + / -0.3 hours.

[0105] At 1 day of aging, except for accelerator composition 1, all the other seven accelerator compositions showed a significant improvement in the unaged ASTM D35 for synthetic rubber surgical gloves, both aged and unaged. Molded and chlorinated gloves that meet the tensile strength requirements of 77 were obtained. Examples 9 and 10, containing only DIXP or HA, did not meet the tensile strength requirements. .

[0106] When no HA was included and a high level of DIXP of 5.0 phr was used (Example 9), the unaged The tensile strength of the glove (aged for 2-3 days) is low for molded gloves (4.0-4.8MPa), and chlorine-treated gloves The gloves were 3.9 to 7.5 MPa. 0.5 phr of high-level HA was used, and DIXP Even when not using (Example 10), the tensile strength of the unaged specimen (aged for 2-3 days) was The pressure was low (0.4 MPa) for gloves and 0.4 to 1.3 MPa for chlorine-treated gloves. Therefore, enhancer compositions containing only DIXP or only HA, even at high levels, Low tensile strength that fails to meet the requirements of ASTM D3577 for surgical gloves Give characteristics.

[0107] However, surprisingly, the DIXP at 5.0 phr and the very low 0.05 phr When combining levels of HA (Example 1), unaged tensile strength (aged for 2-3 days) The resistance of molded gloves is 17.3 to 22.7 MPa, and that of chlorinated gloves is 22.4 to 24.7 Mpa. These tensile properties increased dramatically from 0.2 to 0.4 Pa. These results clearly demonstrate the strong synergy between DIXP and HA. is shown in.

[0108] In addition, when a high level of HA (0.5 phr) was used without DIXP (Example 10), ), unaged tensile strength (aged for 2-3 days) is low (0.4MPa) for molded gloves, For untreated gloves, the values ​​were 0.4-1.3 MPa. However, again surprisingly, the values ​​were 0.50 p The combination of 0.50 phr of HA and 0.50 phr of low-level DIXP (Example 8) Tensile strength (2-3 days aging) is 18.4-20.5MPa for molded gloves and 18.4-20.5MPa for chlorine-treated gloves. The pressure in the bag increased dramatically to 20.1-21.2 MPa.

[0109] Physical properties of natural rubber polyisoprene gloves

[0110] Tensile Strength of Natural Rubber (Polyisoprene) Surgical Gloves as Described in ASTM D3577 The strength standard is higher than that of synthetic rubber (polyisoprene) surgical gloves, and is unaged. The composition of the present invention has a compressive strength of 24 MPa or more, and after accelerated aging, a compressive strength of 18 MPa or more. It has also been found to work very well with polyisoprene. In fact, the accelerator composition of the present invention As discussed in Examples 11-16 below, these high performance composites for natural rubber polyisoprene are High tensile strength specifications at lower levels of DIXP and HA (synthetic rubber-based polyisoprene) (compared to

[0111] In Examples 11-16, the enhancer compositions (Table 3) contained various levels of HA (0.05-0.2 5 phr) with various levels of DIXP (0.50-3.0 phr). nothing.

[0112] The tensile strength properties of the films of Examples 11-1 are shown in Table 5. [Table 5]

[0113] Natural rubber as described in "ASTM D3577-09 Standard Specification for Rubber Surgical Gloves" The standard for the tensile strength of surgical gloves manufactured by this company is 24 MPa or more before aging and 24 MPa or more after accelerated aging. It is 18MPa or more.

[0114] From Table 5, except for accelerator composition 15 (Example 15) in aging the compounded latex for 1 day, All accelerator compositions for aging compounded latex for 1 to 7 days were Obtaining gloves that meet ASTM D3577 tensile strength specifications for PET surgical gloves This shows that the powdered (i.e. molded) sample and the powder-free (i.e. chlorine) sample can be Processing) samples, both pre-aging and accelerated aging of samples It can also be applied later.

[0115] residual DIXP

[0116] Example 1 (synthetic polyisoprene, 5.0 phr DIXP, 0.05 phr HA), Example 2 (synthetic polyisoprene, 3.0 phr DIXP, 0.075 HA) and Example 11 ( Natural rubber polyisoprene, 3.0 phr DIXP, 0.05 phr HA) For samples from the bags (i.e., without the chlorination step), residual DIXP was analyzed by UV spectroscopy and The HPLC method was used for testing.

[0117] The molded glove was extracted with spectroscopic grade hexane and the UV spectrum of the hexane extract was analyzed. The results showed that there was no residual DIXP from the gloves molded from all three cases. .

[0118] For HPLC analysis, the hexane from the hexane extract was evaporated and the residue was diluted 50:50 When dissolved in a mixture of dichloromethane / methanol and then analyzed using HPLC, The results again showed that there was no residual DIXP in the gloves molded from all three examples. It was shown that.

[0119] These results confirmed that DIXP is indeed transient. is 1 ppm.

[0120] Of course, the above description is given by way of example only and is not intended to be limiting unless otherwise specified, without departing from the scope of the present invention. It will be appreciated that various modifications may be made.

[0121] Throughout this application, various patents and publications are cited. These patents and publications The entire disclosure of this application is hereby incorporated by reference in order to more fully describe the state of the art to which this invention pertains. is incorporated into this application.

[0122] The present invention relates to various alternative embodiments, each of which is equivalent in form and function, as will be apparent to one of ordinary skill in the art having the benefit of this disclosure. Reasonable variations, modifications, and equivalents can be made.

[0123] The present invention has been described in terms of what are presently considered to be the preferred embodiments. On the contrary, the invention is not intended to be limited in any way to the spirit and scope of the foregoing detailed description. It is intended to cover various modifications and equivalent arrangements included within the scope of this disclosure.

[0124] The above description is provided to enable one of ordinary skill in the art to practice the various embodiments described herein. Various modifications to these variations will be readily apparent to those skilled in the art. The general principles defined herein may be applied to other embodiments. Various prominent embodiments described throughout this disclosure that are known or that later become known All structural and functional equivalents to the elements are expressly incorporated herein by reference. Can be enjoyed.

Claims

1. A sulfur source; at least one fugitive dihydrocarbyl xanthogen polysulfide promoter; at least one aldehyde-aniline condensate; A metal oxide; 1. A vulcanizable composition comprising:

2. 10. The vulcanizable composition of claim 1 which is free of non-transient accelerators.

3. Dithiocarbamates, thiurams, thiazoles, guanidines or thioureas as accelerators 2. The vulcanizable composition of claim 1, which is free of dimethylformamide.

4. Only one transient dihydrocarbyl xanthogen polysulfide accelerator and only one and an aldehyde-aniline condensate, does not contain additional compounds that act as accelerators for vulcanizing elastomers; 2. The vulcanizable composition of claim 1.

5. the sulfur source comprises elemental sulfur; The at least one transient dihydrocarbyl xanthogen polysulfide promoter is Contains diisopropyl xanthogen polysulfide, The at least one aldehyde-aniline condensate is a heptaldehyde-aniline condensate. Including, The metal oxide may be selected from the group consisting of zinc oxide, magnesium oxide, lead oxide, and combinations thereof. Selected from the group consisting of:

2. The vulcanizable composition of claim 1.

6. The sulfur source may be elemental sulfur and sulfur donors with low allergenic potential, and combinations thereof; The at least one transient dihydrocarbyl xanthogen polysulfide promoter is Diisopropyl xanthogen polysulfide (DIXP), diisopropyl xanthogen Disulfide, Diisopropylxanthogen Trisulfide, Diisopropylxanthogen Diisopropyl xanthogen tetrasulfide, diisopropyl xanthogen pentasulfide, diisoamylxanthate diisoamyl xanthogen trisulfide, diisoamyl xanthogen tetrasulfide, diisoamyl chi Xanthogen pentasulfide, diethylxanthogen tetrasulfide, dibutylxanthogen dibutyl xanthogen tetrasulfide, dibutyl xanthogen disulfide, and combinations thereof and 2. The vulcanizable composition of claim 1.

7. 10. The vulcanizable composition of claim 1, which is free of additional xanthate compounds.

8. The sulfur source is provided in the range of about 0.5 to about 3 dry parts per 100 dry parts of rubber. R, The at least one dihydrocarbyl xanthogen polysulfide accelerator is 0.5 to 5 parts by dry weight per 0.00 parts by dry weight, The at least one aldehyde-aniline condensate is present in an amount of about 100 parts by dry weight of rubber. provided in the range of 0.05 to about 0.5 phr; The metal oxide is present in an amount ranging from 0.1 to about 2 parts by dry weight per 100 parts by dry weight of rubber. To be prepared, 2. The vulcanizable composition of claim 1.

9. The sulfur source is provided in the range of about 1.0 to about 1.5 dry parts by weight per 100 dry parts by weight of rubber. Obtained, The at least one dihydrocarbyl xanthogen polysulfide accelerator is 00 dry weight parts, The at least one aldehyde-aniline condensate is present in an amount of about 100 parts by dry weight of rubber. provided in the range of 0.10 to about 0.25 phr; The metal oxide is in the range of 0.2 to about 0.8 parts by dry weight per 100 parts by dry weight of rubber. Provided in the surrounding area, 9. The vulcanizable composition of claim 8.

10. 10. An elastomeric article formed with the vulcanized composition of claim 1, said composition comprising: The elastomeric article is free of non-transient accelerators.

11. 11. The elastomeric article of claim 10, wherein the elastomeric article contains less than 1 ppm residual DIXP. Stomach products.

12. 8. An elastomeric article formed using the vulcanized composition of claim 7, comprising: -EP1131336A1 - An elastomeric article comprising an elastomeric article, the article being free of additional compounds that act as accelerators for vulcanizing the elastomeric article 。

13. The elastomeric article may be used in the manufacture of gloves, probe covers, finger cots, catheters, dental dams, etc.

13. The elastomeric article of claim 12, wherein the elastomeric article is selected from the group consisting of: and a condom.

14. The elastomeric article of claim 12, wherein the elastomeric article is powder-free.

15. Elemental sulfur, diisopropyl xanthogen polysulfide; Heptaldehyde-aniline, A metal oxide; A vulcanizable composition comprising:

16. Polyisoprene, Elemental sulfur, diisopropyl xanthogen polysulfide, heptaldehyde-aniline and a vulcanized composition comprising a metal oxide; 1. A latex dispersion comprising:

17. No additional compounds functioning as accelerators for vulcanizing the elastomer.

17. The latex dispersion according to 16.

18. Method for preparing polyisoprene elastomer articles with reduced allergenic potential It is a law, Providing the latex dispersion of claim 16; The latex dispersion is coated onto a former by coagulant dipping to form a first elastomeric layer. and drying and vulcanizing the first elastomeric layer; A method comprising:

19. coating the former coated with the first elastomeric layer with a second latex dispersion; forming a second elastomeric layer by The second elastomeric layer is applied prior to drying and vulcanizing the first elastomeric layer. Used, 20. The method of claim 18.

20. The second elastomeric layer has the same composition as the first elastomeric layer.

20. The method according to claim 19.

21. the second elastomer layer has a different composition than the first elastomer layer.

20. The method according to claim 19.

22. The second elastomer layer is made of natural rubber, polyurethane, polybutadiene, polychloro Polypropylene, nitrile rubber, block copolymers of styrene and butadiene, styrene and isopropyl a block copolymer of ethylene, and a synthetic polyisoprene; 20. The method of claim 19, formed from a latex dispersion further comprising a polymer latex. method.

23. 1. A coating composition for an elastomeric article, comprising: The latex dispersion of claim 16; Natural rubber, polyurethane, polybutadiene, polychloroprene, nitrile rubber, styrene block copolymers of styrene and isoprene, and a second polymer latex selected from the group consisting of synthetic polyisoprene; Water, Including, The total solids content of the coating composition is from about 3% to about 15%. A coating composition for an elastomeric article.

24. The second polymer latex is selected from the group consisting of nitrile and synthetic polyisoprene. The coating composition of claim 23 .

25. 17. An elastomeric article formed with the latex dispersion of claim 16, comprising: The elastomer is free of additional compounds that act as accelerators for vulcanizing the elastomer. Mer goods.

26. 24. An elastomeric article formed with the coating composition of claim 23. , which does not contain additional compounds that act as accelerators for vulcanizing the elastomer tomer goods.

27. The elastomeric article may be used in the manufacture of gloves, probe covers, finger cots, catheters, dental dams, etc. and condoms; The elastomeric article is powder-free.

26. The elastomeric article of claim 25.

28. The elastomeric article may be used in the manufacture of gloves, probe covers, finger cots, catheters, dental dams, etc. and condoms; The elastomeric article is powder-free.

27. The elastomeric article of claim 26.

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