Vulcanization composition for reducing allergen potential and elastomer article formed using the same

Abstract

The present invention provides a coating composition for elastomer articles. [Solution] The present invention provides a method for producing a latex dispersion, comprising: providing a rubber component containing polyisoprene; and combining the rubber component with a vulcanization composition containing at least one transient dihydrocarbyl xanthogene polysulfide accelerator and at least one aldehyde-aniline condensate. The present invention also provides a coating composition for elastomer articles, comprising the latex dispersion; a second polymer latex selected from the group consisting of natural rubber, polyurethane, polybutadiene, polychloroprene, nitrile rubber, styrene-butadiene block copolymer, styrene-isoprene block copolymer, and synthetic polyisoprene; and water.

Description

Technical Field

[0001] Cross - reference to related applications This application claims priority to U.S. Patent Application No. 16 / 216, without prejudice, filed on December 11, 2018 No., and this application claims priority to U.S. Provisional Patent Application No. 62 / 598,048, filed on December 13, 2017. The titles of both applications are "Vulcanization Composition for Reducing Allergenic Potential and Elastomeric Articles Formed Therewith". The disclosure of each priority application is hereby incorporated by reference in its entirety into this specification. ULCANIZATION COMPOSITION FOR REDUCING AL LERGENIC POTENTIAL AND ELASTOMERIC ARTIC LES FORMED THEREWITH)". The disclosure of each priority application is hereby incorporated by reference in its entirety into this specification. LERGENIC POTENTIAL AND ELASTOMERIC ARTICLES FORMED THEREWITH)". The disclosure of each priority application is hereby incorporated by reference in its entirety into this specification. in its entirety.

Background Art

[0002] The present invention generally relates to vulcanized compounds, and more specifically to a vulcanization composition having a reduced allergenic potential, including an accelerator composition for vulcanizing elastomeric articles. ​​​​​​​​​​​​​​​​​​​ Symptoms include swelling, watery eyes, rhinitis, asthma, and, in very rare cases, anaphylactic shock. Type I allergy Lugia is associated with residual extractable proteins present in natural rubber latex products. ru.

[0005] Water leaching, chlorination, and low protein or deproteinization Seeds to reduce extractable proteins in latex gloves, such as the use of crystalline latex. Various technologies are available. However, some people are allergic to natural rubber latex proteins. The use of synthetic gloves is recommended for healthcare workers and patients with certain conditions. The synthetic materials used are polyisoprene, acrylonitrile-butadiene (nitrile), and polyk Contains loloprene (neoprene), polyurethane, and polyvinyl chloride.

[0006] As a result of the incidence of type I reactions in response to contact with natural rubber proteins, in particular, skin and In the manufacture of medical devices that come into contact with the skin, synthetic latex does not contain natural rubber latex proteins. A shift is underway to the use of synthetic materials. Considering cost and performance, synthetic materials are suitable for glove manufacturing. For latex, nitrile latex and polyurethane latex are used for inspection gloves. Examples of materials used for surgical gloves include polychloroprene latex and polyisoprene latex. In surgical gloves, polyisoprene latex has properties similar to natural rubber, especially in terms of tensile strength. Polychrome is expensive because it has extreme stretch, flexibility and a comfortable feel. It is preferred over Loprene.

[0007] However, type IV allergic reactions can be triggered by natural or synthetic elastomer articles. This can occur. Synthetic latex is compounded latex. The use of certain chemicals that may be found in ATEX still causes allergic reactions. It can cause a type IV delayed-type hypersensitivity reaction, which is a cell-mediated allergy to certain chemicals. This is a response. Symptoms first appear 48 to 96 hours after contact. This is a type IV allergic response. Potentially triggering chemicals include thiram, mercaptobenzothiazole, and dithiocarbamate. Salts (dithiocarbamates), diphenylguanidine, and thioureas Which vulcanization accelerators are included, and which are used in the process of preparing elastomer articles? The U.S. Food and Drug Administration (FDA) has found thiazole, thiuram, and carbs in rubber products. Carbamates can induce type IV allergic reactions in humans. They acknowledge this. “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 Era To ensure that residual accelerators in the stoma article are very low, the level of accelerators used is kept to a minimum. It is important to do so.

[0008] Elastomer articles are generally manufactured using a latex immersion process, and this process This involves using a solidifying agent solution (usually calcium nitrate) to form molds or formers. including the step of immersing in an um aqueous solution. After evaporating the solvent, the mold / forming tool coated with a coagulant is immersed in the compounding latex so that a film of coagulated rubber particles is deposited thereon . After gelling the latex film using heat, the wet gelled latex film is leached in water and then dried and vulcanized in a hot air oven. During vulcanization, the rubber molecules are chemically crosslinked

[0009] Most commonly, the crosslinking agent is sulfur. However, sulfur alone is inefficient for forming crosslinks . Conventionally, sulfur has always been used in combination with a vulcanization accelerator and an activator

[0010] A vulcanization accelerator is usually an organic compound that increases the rate and efficiency of sulfur crosslinking, while an activator is a compound that increases the efficiency of the accelerator. Examples of accelerators used in latex compounding include thiuram, dithiocarbamate, mercaptobenzothiazole, diphenylguanidine, and thiourea. After vulcanization, depending on the amount of accelerator used , some or most of the accelerator is chemically bonded to the rubber matrix, but some remains unreacted and may remain as a residue in the finished elastomeric article

[0011] . Vulcanization activators used in latex compounding are usually metal oxides such as zinc oxide, magnesium oxide, and lead oxide

[0012] . Various methods have been attempted to minimize or eliminate type IV allergic reactions caused by vulcanization accelerators, including crosslinking without using sulfur and vulcanization accelerators . Approaches include (a) crosslinking using gamma-ray irradiation, (b) crosslinking using organic peroxides, (c) ​ Crosslinking using only zinc oxide via carboxyl-zinc ion bonding, and (d) formation This includes the introduction of functional groups into a polymer backbone that can form crosslinks after the product has been manufactured. In short, all of these approaches have drawbacks. For example, (a) and (b) The approach yields products with lower physical properties and lower aging resistance than sulfur-cured products. vinegar.

[0013] Another approach is the use of safer accelerators. These have a potency for allergens. It is a stimulant with a lower saturation. For example, zinc dibenzyl dithiocarbamate (zinc dibenzyl dithiocarbamate (ZBEC), diisononyl dithio Zinc diisononyl dithiocarbamat e) Using high molecular weight promoters with low allergen potential, such as (ZDNC) Yes, it is possible. Due to their high molecular weight, these types of accelerators are suitable for natural rubber and synthetic polyisopropyl alcohol. It is more compatible with rubber and therefore has higher dissolution in the rubber matrix. It has a degree of bloom. As a result, it blooms on the rubber surface and may cause a potential allergic reaction in contact with the user. Very few high molecular weight accelerators cause a reaction. For similar reasons, extracts from rubber are The amount of high molecular weight promoter obtained is extremely small. ZDNC is preferred over ZBEC, however... This is because ZDNC has a higher solubility in natural rubber (approximately 3% by weight / weight), and ZBE The solubility of C is only about 0.5% by weight.

[0014] A further approach involves using a transient accelerator, i.e., one that is completely used during vulcanization and does not remain in the product. The key is to use a combination of accelerators that do not leave any residue. Examples of such transient accelerators include... For example, diisopropyl xanthogen polysulfide (diisopropyl xa Diisopropylxanthogen (DIXP), diisopropylxanthogen Disulfide, diisopropyl xanthogent trisulfide, diisopropyl xanthogent Ntetrasulfide, diisopropylxanthogenpentasulfide, diisoamylxa Electrolyte trisulfide, diisoamyl tetrasulfide, diisoamyl tetrasulfide Santogenpentasulfide, diethylxanthogentetrasulfide, dibutylxane Dihydrocarboxymethyl tetrasulfide, dibutylxanthogen disulfide, and other dihydrocarboxymethyl tetrasulfide compounds. Santhogen polysulfide (dihydrocarbyl xanthogen pol (dialkyl xa) (contains xanthogen polysulfides) [short form "xanthogen polysulfides "Luffy" is one example.

[0015] A typical example using DIXP is that even if DIXP is heated to a high temperature by itself, it does not volatilize or It does not decompose completely into a gaseous product. However, DIXP is also used in diene-containing polymers. When used with sulfur and zinc oxide to crosslink rubber, it is completely consumed. The main reaction products formed are sulfur crosslinks, isopropanol, and carbon disulfide. Ropanol and carbon disulfide volatilize at the crosslinking / vulcanization temperature, so they do not affect the polymer or rubber. It leaves no qualitative residue. DIXP does not contain nitrogen in its chemical structure, so thiram and It is also impossible to generate N-nitrosamines related to dithiocarbamate enhancers. Furthermore, certain nitrosamines are thought to be carcinogenic, and their formation This should be avoided. However, DIXP, when used alone, is particularly harmful to polyisoprene articles. Furthermore, promote sulfur crosslinking to the extent that it generates enough sulfur crosslinks to produce useful products. No. The resulting article will have too low a tensile strength. Therefore, DIXP always uses other methods. It is used in combination with other medications.

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

[0017] term

[0018] 1.0 phr of the component is equivalent to 100 parts dry weight of rubber. (GHT rubber) contains 1.0 dry weight (1.0 part dry weight) of its components per unit. It means weight.

[0019] Abbreviation: DIXP - Diisopropyl xanthogen polysulfide n polysulfide), TMTD-tetramethylthiuram disulfide (tetramethylthiuram disulfide), ZMBT-mercaptobenzothiazo zinc le), ZDBC-zinc dibutyl dithiocarbamate, ZDEC - Zinc diethyl dithiocarbamate, DPG -diphenyl guanidine, ZDNC-diisononyldithiocarb Zinc diisononyl dithiocarbamate, MBT-mercaptobenzothiazo (mercaptobenzothiazole), SDBC-dibutyldithiocarbamate sodium (sod Sodium diethyldithiocarbamate (s) Sodium diethyl dithiocarbamate, SIX-isopropylxanthogenic sodium (s Zinc isopropyl xanthate (zinc isoprop (yl xanthate).

[0020] Stevenson's U.S. Patent No. 4,695,609 is for dihydrocarbyl xanthoglycerides. Genpolysulfide (1.5-4 phr DIXP) and metal hydrocarbyl xant Originate (metal hydrocarbyl xanthate) (0.05~5phr isopropyl / isobutyl) Vulcanizable material containing zinc luxanthogenicate and less than 0.4 phr of nitrosaturable material This invention discloses an accelerator system used to cure a rubber composition.

[0021] Stevenson's U.S. Patent No. 5,254,635 is for dihydrocarbyl xanthoglycerides. Genpolysulfide (1-6 phr), dibenzylthium sulfide (maximum 1.5 phr) r) xanthate compounds (0-5 phr) and less than 0.2 phr This invention discloses a sulfur-free rubber vulcanizable composition containing a nitrosable material.

[0022] Saks' U.S. Patent No. 6,618,861 is for 2 phr TMTD, 0.2 phr ZMBT, 0.2 phr ZDBC, 0.2 phr diphenylthiourea and 0.2 phr The present invention discloses a polyisoprene composition comprising an accelerator system containing hr ZDEC.

[0023] Lucas et al., U.S. Patent Application Publication 2003 / 0161975, describes a defect-free poly To manufacture Soprene condoms, tetrabenzyl thiuram disulfide or ZB Along with the EC, it is disclosed that sulfur and DIXP are used. This latex compound Wound is a conventional product containing zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, etc. The stability is improved compared to latex formed using the accelerator. The accelerator composition , 1.5 phr of DIXP and 0.6 phr of tetrabenzyl / tetraethyl thiuramdi It contains sulfides.

[0024] Wang et al.'s U.S. Patent Nos. 6,828,387 and 8,273,810 are from the United States. Polyisotherapy using an accelerator composition containing occarbamate, thiazole, and guanidine The formulations for pren are disclosed, where each dry weight is approximately 0.50 to approximately 1.00 phr. This is within the range. Example 1 uses 0.50 phr of ZDEC and 0.50 phr of ZMBT. The following is an overview of the accelerator composition containing 1.00 phr of DPG.

[0025] The synergistic combination of DIXP and ZDNC is effective for natural rubber latex and synthetic polyiso It is recommended as a safer accelerator for use with plain latex. Kraborty et al., "New Sustainable Development for Latex Applications" "Latest Information on Promoters" - International Latex Conference (2005)(“Novel Sustainable Accelerators for Latex Applications-Update,” International Latex Conference (2005)).

[0026] Conventional curing packages for vulcanizing polychloroprene use sulfur and non-transient accelerators. , and zinc oxide. The non-transient accelerator used is dibutyldithiocarbamate. Zinc (ZDBC); tetraethyl thiuram disulfide and dibutyl dithiocarbamate Thorium mixture; and diphenylthiourea (thiocarbanilide) and diphenylguani Contains a mixture of gin (Carl, Neoprene Latex, chapter 3, published by EI, du Pont de Nemours& See Co. (1962). However, residues of these non-transient promoters in the product are IV It may trigger a type of allergic reaction.

[0027] Chakraborty et al. (2nd International Rubber Glove Conference 2004, Kuala Lumpur, M) Lesia(2nd International Rubber Glove Conference 2004, Kuala Lumpur, Malaysia )) is sulfur, two combinations of two accelerators (ZDNC and DIXP, or ZDEC and M Uses BT), zinc oxide, and two antioxidants (AO2246 and MMBI). The prescription is disclosed. Chakraborty et al. have developed a safer formula for PI latex. The document discloses an accelerator system and a conventional accelerator system. The former system is 0.4p Includes hr DIXP and 0.4 phr ZDNC, the latter system is 0.5 phr ZD Contains EC and 0.5 phr of MBT. For DIXP / ZDNC compositions, formulated latex The latex film is aged at 30°C for 8 days before it acquires good tensile strength properties. It is necessary to do so. The test film is made by casting latex onto a glass plate. It is prepared and dried at ambient temperature before curing. This film formation method is called "coagulant immersion (coa This method differs from the method used in the commercial production of gloves (gulant dipping).

[0028] Virdi et al. (8th International Rubber Glove Conference and Exhibition 2016, Kuala Lumpur, M) Lesia(8th International Rubber Glove Conference and Exihition 2016, Kuala Lu The presentation (in mpur, Malaysia) was presented by DIXP (0.5phr) and ZDN. C(0.5phr) is replaced with a metal xanthogenic salt (0.3 SIX or 0.3 ZIX). Disclosed is an accelerator composition for synthetic polyisoprene that includes in combination with, ASTM D3577 standard for rubber surgical gloves (Type II synthetic latex gloves) This produces a coagulant-soaked film with a good tensile strength value that can meet the requirements. Tex is matured at 30°C or 35°C for 24 hours before a film forms through immersion in a coagulant. They are also free of metal xanthogenic acid salts and contain 0.5 phr of DIXP and Accelerator composition containing 0.5 phr of ZDNC (developed by Chakraborty et al.) The indicated composition produces a coagulant-soaked film with very poor tensile strength properties. This shows that the film formed by casting onto a glass plate The findings of Chakraborty et al., who discovered that it provides good tensile strength properties, are very different. They are different.

[0029] U.S. Patent No. 7,041,746 of Dzikowiczn is for dithiocarbamate ( (0.5-4.0 phr), thiourea (0.2-4.0 phr), and thiazoyl phosphate (if applicable) An accelerator system for synthetic polyisoprene containing 0.5 phr is disclosed.

[0030] Lucas et al.'s U.S. Patent No. 8,087,412 concerns synthetic polyisoprene articles (cond Pre-vulcanization compositions and post-vulcanization compositions for gloves and other items. This document discloses a post-vulcanization composition, wherein pre-vulcanization The accelerator system includes ZDEC / ZDBC (0.4~1.0 phr), and the post-vulcanization accelerator system The stems are SDBC / SDEC (0.05~0.50 phr) and DIXP / xanthos. Contains nsulfide / thiuram (0.2-0.6 phr).

[0031] Van Jole's U.S. Patent No. 8,673,172 concerns conjugated diene monomers (e.g., A group consisting of polyisoprene and conjugated diene monomers having vinyl aromatic comonomers. A latex accelerator formulation for synthetic rubber latex derived from DIXP, Disclosed is a method using an accelerator composition containing alkyldithiocarbamate and DPG. Here, each of the accelerator compositions is present at a concentration of 0.25 to 1.00 phr.

[0032] Chen et al., U.S. Patent No. 8,980,391, describes the use of sulfur, zinc oxide, and formed vulcanization composition containing a transient accelerator (DIXP) that does not leave detectable residual DIXP in the article. Polychloroprene with low allergen potential, manufactured using [a specific method / product]. The product is disclosed. The manufactured surgical gloves conform to the ASTM D3577 standard. It has a high tensile strength. This is due to the sulfur crosslinking and the reactive tertiary chlorine atoms on the polymer chain. (reactive tertiary allylic chlorine atom This can be achieved using zinc oxide as a catalyst through crosslinking between polymer chains, which is promoted by (s). See Carl, Neoprene Latex, Chapter 3.

[0033] Amarasekera et al.'s U.S. Patent Application Publication No. 2015 / 0128329 states that poly Isoprene polymer, thiourea, benzothiazole sulfenamide, thiazole and The first accelerator includes dithiocarbamate, or a combination thereof, and thiuram or a second accelerator comprising xanthogene polysulfide or a combination thereof Gloves containing a latex composition are disclosed. Three examples are given (Examples 1-3). In this context, non-transient accelerators (thiourea, benzothiazole sulfenamide / thiazole The total level of dithiocarbamate and thiuram was 1.4-1.5 phr. The xanthogene polysulfide level was 0.3 phr.

[0034] Krutzer's U.S. Patent Application Publication 2016 / 0108154 describes a sulfur donor (Chi Thiuram as an accelerator and sulfur donor (Uram is known to function as an accelerator and sulfur donor) 0.5-10 phr and a combination of thiocarbamate or dithiocarbamate 0.05 It is used together with a synthetic isoprene polymer containing polyisoprene, which contains ~2.0 phr. They are disclosing a system for promoting eye growth.

[0035] Aldehydeamines are reaction products of various aldehydes and amines, and in 1910... It is known to be used as a drying accelerator for rubber. Min-promoting agents include aldehyde aniline, butyraldehyde-aniline, and heptaldehyde. It is do-aniline (HA). Currently, the use of aldehyde-amine accelerators is limited. These accelerators can be used with hard rubbers such as ebonite. When using this accelerator, 2.5 phr can be used together with 30-50 phr of sulfur. These are thiazo It can be used as a secondary accelerator at 0.20-0.30 phr along with a sulfenamide accelerator. It is commonly used. (Rubber Compounding: Principle) s,Materials,and Techniques.Second Editio n, by Fred W. Barlow p110, Marcel Dekker, I (nc., New York, 1993). The accelerator used in drying rubber is latex. It can be used with rubber, but its effectiveness and efficiency may not be the same. HA It is not known that it is used in the manufacture of rubber gloves. Curing of dried rubber and latex. The use of "xanthogene polysulfide" in combination with other accelerators to achieve this is St Evenson (US Patent No. 4,695,609; US Patent No. 5,254,635) Disclosed by: The combination of aldehyde-aniline and DIXP has been considered to date. I haven't done that. [Overview of the project] [Problems that the invention aims to solve]

[0036] Therefore, a simpler method is used to vulcanize elastomer articles with a small amount of accelerator. A vulcanizing composition that reduces the potential of allergens, particularly suitable for polyisoprene applications. There is a need for a vulcanization composition for this purpose. The composition of the present invention contains the transient accelerator DIXP and In combination, dithiocarbamate, thiazole, thiram, guanidine, and thiouria This invention combines a small amount of additional accelerator that does not contain conventional accelerators such as ions. Aldehyde-aniline is used as an effective additional accelerator. The present invention also provides vulcanization compositions The present invention relates to polyisoprene-based elastomer articles formed using [a specific material]. The present invention also reduces [a specific material]. Manufacturing a reduced allergenicity vulcanization composition Methods for vulcanizing elastomer articles, and methods for using vulcanizing compositions to vulcanize elastomer articles. . [Means for solving the problem]

[0037] Summary of the Invention Certain aspects of this disclosure relate to accelerator compositions used for vulcanizing elastomer articles. The present invention relates to a vulcanization composition that provides a higher level of non-transient and transient accelerators. Compared to vulcanizing compositions containing the composition, the allergen potential is reduced, Elastomer articles formed using a vulcanization composition having a high level of accelerator composition and In comparison, it is used to form elastomer articles with reduced allergen potential. It can be used. The present invention further produces a reduced allergenic vulcanization composition. The present invention relates to a method and a method for using a vulcanizing composition to vulcanize an elastomer article.

[0038] The present invention relates to a vulcanization composition, a latex dispersion, and an elastomer formed using conventional techniques. vulcanized compositions with reduced or eliminated allergen potential compared to stomer articles. By providing latex dispersions and elastomer articles, we aim to contribute to the field of art. And to satisfy unmet needs in other fields. According to some aspects of the present invention This results in a reduction or elimination of type I and type IV allergenicity. The vulcanization compound of the present invention Products, latex dispersions, elastomer articles, and methods are available for elastomer articles. It is beneficial to avoid problems related to allergic reactions, especially for healthcare providers and Both the patient and the individual frequently and / or over a long period of time are exposed to these potential allergen sources. It is beneficial in the medical field in which it is exposed.

[0039] According to one aspect of the present invention, the present invention relates to a transient xanthogene polysulfide promoter and The present invention relates to a vulcanization composition comprising a combination of aldehyde-aniline accelerators. Another aspect of the present invention According to the present invention, a single transient xanthogene polysulfide enhancer and a single A The present invention relates to a vulcanization composition containing a dehyd-aniline accelerator, wherein the vulcanization composition does not contain additional accelerators. According to another aspect of the present invention, the present invention relates to diisopropyl xanthogene polysulfide This relates to a vulcanization composition containing a heptaldehyde-aniline condensate as an accelerator. According to that embodiment, the vulcanization composition comprises a non-transient accelerator and a higher level accelerator. Compared to sulfur compositions, it exhibits reduced allergenicity.

[0040] In a further embodiment, the elastomer is polyisoprene. Polyisoprene is natural It may be natural rubber polyisoprene or synthetic polyisoprene. In yet another embodiment, Using latex-containing materials, gloves (specifically medical gloves, more specifically inspection gloves) (and surgical gloves), as well as condoms, probe covers, dental dams, finger cots, and Elastomer articles may be formed that may include, but are not limited to, catheters.

[0041] The features, structures, or processes disclosed herein are subject to change without notice. Features, structures, or processes that can be replaced, combined with, or omitted It may be abbreviated. Furthermore, for the purpose of summarizing this disclosure, devices Specific aspects, advantages, and features of are described herein. Some of these advantages include Or all of these may not necessarily be achieved in accordance with the specific embodiments disclosed herein. Please understand that this is not the case. Each aspect of this disclosure is neither essential nor indispensable. stomach. [Modes for carrying out the invention]

[0042] Detailed explanation The detailed descriptions below are intended to describe various configurations and are not included in this specification. The concept described does not represent the only possible configuration in which it can be implemented. A detailed explanation will cover various generalities. It contains specific details to fully understand the concept of "thought." However, these concepts are It will be obvious to those skilled in the art that this can be done without these specific details.

[0043] The present invention generally includes accelerator compositions used for vulcanizing elastomer articles. With respect to the vulcanization composition, the accelerator composition uses a vulcanization composition having a higher accelerator composition. Compared to elastomer articles formed by [method], it has a reduced allergen potential. The vulcanization composition comprises a transient vulcanization accelerator and an additional accelerator. The amount of the additional accelerator is The amount is considerably less than in conventional compositions. The present invention also uses a vulcanizing composition to form The present invention relates to latex dispersions and elastomer articles with reduced a Method for producing allergenic vulcanization compositions, and vulcanization for vulcanizing elastomer articles. This relates to a method of using the composition.

[0044] A transient vulcanization accelerator for use in accordance with the present invention contains a xanthogene polysulfide. Hmm. Diisopropyl xanthogene polysulfide (DIXP), diisopropyl xantho Genisulfide, diisopropylxant gentrisulfide, diisopropylxant Togentetrasulfide, diisopropylxanthogenpentasulfide, diisoamyl Xanthogen trisulfide, diisoamyl xanthogen tetrasulfide, diisoamyl Luxanthogen pentasulfide, diethylxanthogen tetrasulfide, dibutylx Santogen tetrasulfide and dibutylxanthogen disulfide are used in accordance with the present invention. This is a preferred transient xanthogene polysulfide that can be used and may be developed in the future. Further transient xanthogene polysulfides are also present in the present invention's accelerator composition and latex dispersion. It is expected to find applications in the human body and elastomer articles. The vulcanization composition of the present invention In accelerator compositions for substances, transient xanthogene polysulfides are useful, but These are consumed during vulcanization by bonding to the rubber matrix and are used for vulcanization. As a by-product that evaporates at high temperatures, it forms a gas and / or a volatile liquid, and thereafter This is to prevent leaving any residue on the elastomer material. Diisopropylxanthogenpo In the case of risulfide (DIXP), this compound produces isopropyl alcohol as a byproduct. It forms carbon disulfide gas.

[0045] The additional accelerator composition used in the present invention comprises aldehyde-aniline. The adjuvant agents include heptaldehyde-aniline (HA) and butyraldehyde-aniline (B A) is one example, but other aldehyde-anilines may also be used. Specifically, aldehyde Hydaniline is a condensate. In a preferred embodiment, heptaldehyde-aniline (H A) is an additional accelerator.

[0046] This invention is also made from polyisoprene rubber and contains aldehyde-ani as an additional accelerator. Elastomer articles vulcanized with phosphorus and xanthogene polysulfide accelerators To provide. According to some embodiments, elastomer articles are gloves (specifically medical gloves). , more specifically, examination and surgical gloves), as well as condoms, probe covers, teeth Medical dams, finger cots, and catheters may be included. According to one embodiment, such facilitation Polyisoprene surgical and examination gloves are provided, manufactured using a chemical composition.

[0047] Elastomer articles manufactured using large quantities of accelerator compositions, particularly non-transient accelerators, are susceptible to hindrance. The product contains a residual accelerator that can cause a type IV allergic reaction, and uses natural rubber. The manufactured elastomer articles are extractable in relation to type I allergic reactions in humans. Contains latex protein. Elastomer article, accelerator composition, latex according to the present invention. The method for producing the sulfuric acid composition, the accelerator composition, and the method for vulcanizing the elastomer article are based on natural gas. Because it does not contain mu and the level of residual accelerators contained within is not high, it does not cause type I allergies. The likelihood of a reaction and type IV allergic reaction is reduced or eliminated.

[0048] Non-transient accelerator compositions are known to cause type IV allergic reactions in humans. It contains thiazole, thiram, dithiocarbamate, guanidine, thiourea, etc. It is visible.

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

[0050] vulcanization composition

[0051] The vulcanization composition of the present invention preferably comprises a sulfur source, an accelerator composition, and an activator. The accelerator composition may include a transient accelerator and additional accelerators. Allergens of the vulcanization composition According to one aspect of the present invention, the properties of elemental sulfur are minimized or eliminated. l sulfur), single xanthogene polysulfide transient accelerator, zinc oxide, and A single aldehyde-aniline accelerator is used. In rubber technology terminology, a certain component "phr" stands for 100 parts (dry weight) of rubber. (8)) Per serving (dry weight) of that component t)) means. The additional accelerator (aldehyde-aniline condensate) is approximately 0.05 phr ~approximately 0.50 phr, preferably approximately 0.075 phr to approximately 0.35 phr, more preferably The range is approximately 0.10 phr to approximately 0.25 phr. Transient accelerator (xanthogenic polymer Sulfide is approximately 0.50 phr to approximately 5.0 phr, preferably approximately 0.75 phr to approximately Vulcanization composition: 3.0 phr, more preferably in the range of about 1.0 phr to about 2.5 phr. The materials are natural rubber, polyurethane, polybutadiene, polychloroprene (neoprene), and Tolyl rubber, styrene and butadiene block copolymers, styrene and isoprene Block copolymers of polyisoprene, and the above polymers or elastomers This invention can be used to vulcanize elastomers containing combinations or mixtures. In a particular preferred embodiment, the elastomer is polyisoprene. It can be natural or synthetic.

[0052] In some aspects of the present invention, the allergenicity of the vulcanizing composition is minimized or completely eliminated. In this invention, the sulfur source used in the vulcanization composition contains elemental sulfur. According to one aspect of the present invention, In this case, only elemental sulfur is used. The amount of elemental sulfur is about 0.5 to about 3 phr, preferably about 1 to 2 phr. The range is phr, more preferably 1 to about 1.5 phr.

[0053] Sulfurizing activators include zinc oxide, magnesium oxide, lead oxide, and combinations thereof. Examples include, but are not limited to, zinc oxide vulcanized in one embodiment of the present invention. It is used as an activator. The activator is about 0.1 to about 2.0 phr, preferably about 0.1 The value is approximately 1.0 phr, more preferably in the range of approximately 0.2 to approximately 0.8 phr.

[0054] Some of the inventions wherein the allergenicity of the vulcanizing composition is minimized or eliminated as a whole. In that embodiment, one vulcanization accelerator used according to an aspect of the present invention is a transient xane It is a togen polysulfide. According to some embodiments, transient xanthogenic polysulfide A sulfide is a compound with two or more sulfide groups, i.e., three sulfide groups (trisulfide). It has four sulfide groups (tetrasulfide) and five sulfide groups (pentasulfide). It is a polysulfide containing . According to a further aspect of the present invention, transient xanthogene Polysulfides include dihydrocarbyl xanthogene polysulfides (diisopropyl xanthogenes). Diisopropylxanthogen disulfide (DIXP), Diisopropylxanthogen disulfide, Di Isopropyl xanthogen trisulfide, diisopropyl xanthogen tetrasulfide Diisopropyl xanthogen pentasulfide, diisoamyl xanthogen trisulf Id, diisoamylxanthogen tetrasulfide, diisoamylxanthogen pentas Rufid, diethylxanthogen tetrasulfide, dibutylxanthogen tetrasulf Contains dibutylxanthogen disulfide. These transient xanthogen It should be noted that polysulfide promoters can also function as sulfur donors. In one embodiment, the sulfur donor has a low allergen potential.

[0055] The additional accelerator composition used in the present invention may contain an aldehyde amine. More specifically, these aldehyde amines may be aldehyde anilines. Specifically, the additional accelerator is an aldehyde-aniline condensate. The accelerator of the present invention is: Heptaldehyde-aniline (HA) condensate and butyraldehyde-aniline (BA) Condensates are mentioned, but other aldehyde-aniline products may be used. Preferred Embodiment Therefore, heptaldehyde-aniline (HA) is an additional accelerator.

[0056] In one aspect of the present invention, only a single transient xanthogene polysulfide vulcanization accelerator is used to promote Used in the drug adjuvant composition, only a single aldehyde aniline adjuvant is used, and no additional The vulcanization accelerator is also excluded from the accelerator composition.

[0057] According to a further aspect of the present invention, only DIXP and HA are vulcanization accelerators, and these Only the following compounds function as vulcanization accelerators in the vulcanization accelerator composition. Allergens When preparing accelerator compositions with reduced or removed properties according to the present invention, they are advantageous in that It may contain only DIXP and HA. Additional compounds that may also function as vulcanization accelerators may be added. It is excluded from the accelerator composition. In another embodiment, an additional transient accelerator is included in the accelerator composition. This is possible, but additional non-transient accelerators are excluded. In either embodiment, these While the exclusion of is beneficial, it is not possible in the presence of additional vulcanization accelerators or additional non-transient accelerators. Use may cause allergic reactions, especially type IV allergic reactions, with elastomers formed in the vulcanized composition. This is to increase the likelihood of such incidents occurring in users of Tomar products.

[0058] Latex dispersions and elastomer articles

[0059] The vulcanizing composition of the present invention can be used to prepare a latex dispersion. Tex dispersion contains natural rubber, polyurethane, polybutadiene, and polychloroprene (neo Plain, nitrile rubber, styrene and butadiene block copolymer, styrene Block copolymers of isoprene, polyisoprene, and the above polymers or It may include elastomers that can be selected from combinations or mixtures of elastomers. Specific embodiments According to the present invention, a particularly preferred elastomer for use in the latex dispersion is poly It is isoprene. These latex dispersions are used in addition to elastomer and vulcanization compositions. It may also contain one or more different non-curing components. Non-curing components include antioxidants, ammonium compounds, and ammonium compounds. Examples include, but are not limited to, stabilizers, plasticizers, anti-ozone agents, pigments, and fillers. According to one embodiment of the invention, when manufacturing an elastomer article (for example, U.S. Article 81102 As described in U.S. Patent No. 66 or 6828387, both of these are The total solids content of the latex dispersion (the entirety of which is incorporated herein by reference) is The range is approximately 25% to 49%.

[0060] The latex dispersion of the present invention, which contains an elastomer and a vulcanizing composition, is suitable for gloves, specific applications. This involves preparing elastomer articles such as medical gloves, and more specifically, examination and surgical gloves. It can be used in a method for doing so. However, a person skilled in the art would know this specification Using the guidance provided in the book, condoms, probe covers, dental dams, finger swabs Other elastomer articles besides gloves, including but not limited to catheters, etc. It is thought that it can be prepared.

[0061] The elastomeric Tomar articles can be manufactured using conventional manufacturing methods, such as immersion in a coagulant. In the "anode" coagulant immersion process, the coagulant-coated molding tool is immersed in a dispersion. The product is formed by soaking and then hardening. "Teague" solidifying agent immersion process In the process, the molding tool is immersed in a dispersion, then immersed in a solidifying agent, and then cured to produce the finished product. These methods form a dispersion containing an elastomer, thereby forming the finished product. It utilizes the body. Preferred elastomers include natural rubber, polyurethane, and polybutadiene. Polychloroprene (neoprene), nitrile rubber, styrene and butadiene block Examples include copolymers, styrene-isoprene block copolymers, and polyisoprene. It is possible. In certain embodiments, a particularly preferred elastomer is polyisoprene. In another embodiment, using a vulcanizing composition comprising sulfur, zinc oxide, HA, and DIXP A vulcanized polyisoprene elastomer article is provided.

[0062] HA had not been used in rubber gloves until now. This invention relates to rubber gloves before aging. The ASTM 3577-09 standard requirements for surgical gloves (natural rubber) are 24 MPa (minimum) and ASTM D for synthetic rubber surgical gloves before aging (18 MPa) and before aging. 17 MPa (minimum) and 12 MPa (minimum) after aging, as per the 3577-09 standard requirements. To obtain an elastomer article having a tensile strength that satisfies the requirements, sulfur, zinc oxide, HA and Polyisoprene latex can be vulcanized using a vulcanization composition consisting of DIXP. This was discovered unexpectedly. DIXP is a transient xanthogene polysulfide, Since no DIXP residue remains on the gloves after vulcanization, and the amount of HA required is small, this vulcanized product is used. Gloves manufactured using this method exhibit a low allergen potential.

[0063] The elastomer article of the present invention can be used when forming an elastomer article. It can be formed using a latex dispersion containing any additive component, the additive component being: Curing components and non-curing components, described later, having the same, similar, or different chemical structure as the elastomer. The total amount of additives used may include at least one of the following: 1, 2, and additional polymers. The amount is approximately 0.5 to 49% by weight of the total dispersed phase solid.

[0064] When curing with sulfur, the main curing agent is preferably elemental sulfur and / or ether. The present invention includes a sulfur donor with low or no rugen potential. In this case, only elemental sulfur is used.

[0065] Examples of activators include zinc oxide, magnesium oxide, and lead oxide, but these Not limited to, zinc oxide is the most commonly used vulcanizing agent. In one embodiment, Zinc oxide is used as an activator.

[0066] The vulcanization accelerator according to the present invention is a transient xanthogene polysulfide and an aldehyde- It is dilin. According to a further aspect of the present invention, the transient xanthogene polysulfide is It is diisopropyl xanthogenic polysulfide (DIXP). Other xanthogenic polysulfides Sulfide or dihydrocarbyl xanthogene polysulfide (dialkyl xanthogene) (Containing polysulfides) diisopropylxanthogen disulfide, diisopropyl Luxanthogen trisulfide, diisopropyl xanthogen tetrasulfide, diiso Propyl xanthogen pentasulfide, diisoamyl xanthogen trisulfide, di Isoamylxanthogen tetrasulfide, diisoamylxanthogen pentasulfide Diethyl xanthogen tetrasulfide, dibutyl xanthogen tetrasulfide, di It contains butylxanthogen disulfide. In one embodiment, aldehyde-aniline is It is HA.

[0067] In this invention, elastomer dispersion formulations Any non-compounding formulations that have been conventionally used A curing component can be used. For example, non-curing components include antioxidants, stabilizers, Examples include, but are not limited to, plasticizers, anti-ozone agents, pigments, and fillers.

[0068] The appropriate antioxidants that can be added to the elastomer dispersion are limited to the following: However, there is no butylated hydroxytoluene (2,6-di-t-butyl-4-methylpheno (Lu) and thiodiethylenebis-di-t-butyl-4-hydroxyphenylpropionate Butylation of hindered phenols such as p-cresol and dicyclopentadiene Hindered polyphenols such as reaction products, trimethyl-tris(di-t-butyl-4) -Hydroxybenzium)-benzene or octadecyldi-t-butyl-4-hydroxy Hindered phenols / hindered polyphenols such as phenylpropionate, 6P Blend of PD with methylstyrene and bis-α-dimethylbenzyldiphenylamine Amines such as mercaptotalamimidazole zinc / phenol mixtures, triazi Triazinon derivatives such as non-phenol mixtures, poly(m-anisidine) and other poly Phenol antioxidant hydrazides such as aromatic amines and phenols having anhydrous copolymers , pheno phenol such as 2,2'-methylene-bis-(4-methyl-6-t-butylphenol) Crysol, 2,4-dimethyl-6-(1-methylcyclohexyl)-p-cresol, etc. This includes resol and styrene-modified phenol. One particularly preferred antioxidant is This is a butylation reaction product of p-cresol and dicyclopentadiene (for example, Wi ngstay L).

[0069] Also, colloidal stabilizers such as alkalis for pH adjustment, surfactants, sodium caseinate, etc. Alkaline casein salts may be added to the aqueous phase.

[0070] Suitable plasticizers that can be added to elastomer dispersions include fatty acids, mineral oils, and Examples include, but are not limited to, ester plasticizers.

[0071] According to some embodiments, elastomers used to manufacture the elastomer articles of the present invention An anti-ozone agent is added to the stomacher dispersion. Ozone is highly ozone-resistant, such as polyisoprene. Some elastomer articles, such as those formed from saturated polymers, are subjected to intense stress. It can be damaged. When contained in the aqueous elastomer dispersion of the present invention, wax, EPDM and Certain high molecular weight polymers, such as hydrogenated polydienes, exhibit excellent osophobicity in such articles. It can provide protection. The wax forms a physical barrier on the surface of the rubber, blocking ozone. Protects against attacks. The wax contains linear paraffin wax and branched microcrystalline There are two types of phosphorus (microcrystalline) wax. The most widely used The anti-ozone wax contains paraffin and provides maximum protection across a wide range of exposure temperatures. It is a mixture of microcrystalline waxes. The paraffin wax is approximately 20-50 pieces. It is a straight-chain hydrocarbon molecule containing carbon atoms. Suitable paraffin wax contains approximately 50 to 7 It has a melting point of 5°C, preferably 52 to 68°C. Microcrystalline wax is non Also known as crystalline wax, it is a hydrocarbon, similar to paraffin wax, but carbon The elementary chains are branched and have a higher molecular weight, with approximately 40 to 70 carbon atoms per chain. Another example of an anti-ozone agent that can be used in the present invention is N-1,3-dimethylbutyl Alkyl / aryl p-phenylenediamine such as -N'-phenyl-p-phenylenediamine 6PPD Contains smectite containing phenylenediamine and alkyl-aryl-p-phenylenediamine. Organic clay anti-ozone agent complexes such as clay, N,N-disubstituted para-phenylenediamine, 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- Examples of p-phenylenediamines include p-phenylenediamine (IPPD), but These are not the only options. In addition, paraffin wax (MW=300~500), micro Crystalline wax (MW=600~700) (along with paraffin wax) and low Polymers containing waxes such as MW PE wax (MW = 100-1100), and polymers. High molecular weight anti-ozone agents such as diphenyldiamine, as well as EPDM and brominated isobutylene / Ozone-inert polymers such as para-methylstyrene copolymer (BIMSM) are used as anti-ozone agents. It can be used as such. 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 can be added to aqueous elastomer dispersions include titanium dioxide and iron oxides. It may include a wide range of natural and synthetic pigments.

[0073] Suitable fillers that can be added to aqueous elastomer dispersions include clay and carbonic acid. Inorganic fillers such as calcium, talc, and silica, as well as cross-linked polymethyl methacrylate. Rate, finely divided urethane resin particles, and polyethylene microspheres, etc. Examples include, but are not limited to, organic fillers.

[0074] Additional polymers are also incorporated into the latex dispersions and elastomer articles of the present invention. This may provide additional functionality, or latex dispersions and elastomers. This may be done to impart beneficial properties to the product. Such functions / properties may be improved. Dampening / wet wearing conditions, improved water repellency. This may include, but is not limited to, improved microbial resistance and improved degradation resistance. It is not the case that... According to some aspects of the present invention, the additional polymer is natural rubber, poly Urethane, polybutadiene, polychloroprene (neoprene), nitrile rubber, styrene and block copolymers of butadiene, styrene and isoprene - and selected from polyisoprene.

[0075] According to some aspects of the present invention, an elastomer article comprising a plurality of elastomer layers is provided. The multiple elastomer layers provided may have the same or different compositions. For example, A coating containing synthetic polyisoprene blended with polychloroprene. Applied to Loprene elastomer articles, it provides improved wearability in wet / squeezed conditions. It can be provided. Another example is a coat containing nitrile mixed with polychloroprene. The coating composition is applied to a polychloroprene elastomer article to improve the wettability of the article. / It can provide wearability in a wet state. In another example, it can be mixed with polyisoprene. A coating composition containing nitrile is applied to a polyisoprene elastomer article. This can provide the article with improved wearability in wet / squeezed conditions. In another example, A coating composition containing polyisoprene blended with acrylate is provided. When applied to a len elastomer article, it provides the article with improved wearability in wet / squeezed conditions. This is possible. For example, an elastomer article has multiple layers of polyisoprene. ru.

[0076] According to a further aspect of the present invention, the elastomer article is made of powder or den. It can be formed with or without powder. Powder and starch are commonly used. Although it is a donning agent, it may be associated with allergic reactions. Yes, and therefore another aspect of the present invention relates to powder- and starch-free elastomer articles. In a further embodiment, less than 5 mg of powder or starch, preferably less than 3 mg of powder or This is starch, more preferably less than 2 mg of powder or starch, most preferably less than 1 mg. Substantially powder-free or starch-free powder or starch-free This relates to (starch-free) elastomer articles. These articles are vulcanized as described above. It is prepared using the composition.

[0077] These and other aspects of the present invention can be further described in the non-limiting embodiments below. It will be explained.

[0078] Glove preparation

[0079] Synthetic polyisoprene or natural rubber polyisoprene gloves are used with a standard coagulant immersion method. Table 1 shows the base compound formulations. (ion) is used as an accelerator composition for synthetic polyisoprene (Table 2) or natural rubber polyiso It was prepared in combination with the accelerator composition for prene (Table 3).

[0080] The following preparations can be used (see, by reference, Japanese Patent No. 8110266 and 68 (Incorporating the entirety of Patent No. 28387) Any standard immersion process is applicable. be.

[0081] The vulcanization composition consists of synthetic polyisoprene latex and a colloidal stabilizer (potassium ricinoleate). Potassium hydroxide (which also acts as a pH adjuster), crosslinking agent (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 components were stirred into polyisoprene latex. Add while doing so. Various components are suitable for latex, as is customary in latex technology. It is in the form of an aqueous solution or aqueous dispersion. Therefore, the water-soluble component is dissolved in water. It is added as an aqueous solution, and the water-insoluble solid component and water-insoluble liquid component are dispersed in water to form an aqueous solution. Add as a powder. After adding all the ingredients, add water and mix the latex mixture for approximately 35 minutes. Dilute to % total solids, and adjust the pH of the latex to approximately 11 for synthetic polyisoprene. For natural rubber polyisoprene, adjust to approximately 10.

[0082] Stir the fully compounded latex and it is ready for immersion. It is then aged at an ambient temperature of approximately 28°C to 32°C.

[0083] Preparation of powder-free gloves

[0084] To evaluate different latex compositions, solidification is performed using ceramic molds (or molding tools). The gloves are prepared by immersion in the solution.

[0085] Preheat a clean ceramic mold to 55-58°C in a hot air oven. Calcium (as a release agent, approximately 4.0-5.0%) and Surfynol TG (as a wetting agent, approximately A calcium nitrate coagulant aqueous solution (55-58°C, specific gravity approximately 1.130) containing 0.15% Immerse. Dry the mold coated with the coagulant in an oven (60°C for about 10 minutes), then latte Immerse in the latex composition. If the total solids content of the latex composition is 33.5%, The residence time in the tex is approximately 15 seconds. As a result, the dry film thickness is approximately 0.20 mm. (To obtain this film thickness, the residence time and the total latex solids content are varied.) (This can be done). The latex film on the mold is suspended in the air for about 5 minutes, and the latex film The film allows for the formation of a good gel. Then, the latex film is applied for about 60 minutes. Immerse in warm water at °C for 5 minutes to leach out water-soluble substances such as calcium nitrate and surfactants. The agent is leached out. The film on the mold is suspended vertically at ambient temperature and dried for about 5 minutes. Next, place the film in the oven and dry and cure it at 135°C for 30 minutes. The temperature and time can be adjusted to obtain the desired properties. After vulcanization, the gloves should be left to approximately ambient temperature. After cooling and lightly coating the film with modified starch, peel the glove from the mold and turn it inside out. Gloves coated with powder are called molded gloves.

[0086] Chlorine treatment

[0087] To produce powder-free gloves, the gloves are post-treated with chlorine. To manage.

[0088] Turn the gloves inside out so that the surface that did not come into contact with the mold during immersion is now on the outside of the gloves again. Chlorine treatment uses approximately 300 ppm of available chlorine (ranging from 200 to 700 ppm). Before chlorine treatment in a chlorine aqueous solution containing (which can be used), pre-wash the gloves with water. Then, after neutralizing the excess chlorine with a sodium hydroxide solution, wash with water (this step The process consists of several steps. The chlorine level is measured on both sides of the finished gloves. It can be adjusted to give the surface desired properties such as reduced friction and stickiness. Next, Partially dry the gloves, then turn them inside out by hand and let them dry further.

[0089] Lubrication

[0090] For good wear with wet or damp hands, dry the gloves before putting them on. It is then transferred to a tumbling washer for a further lubrication process following the chlorine treatment step. This lubrication process involves approximately 1.0% cetylpyridium chloride and 1.0% silicone emulsion. Gloves with an aqueous solution containing Lujon and a 1.5% alkyl phosphate ammonium salt. This includes tumbling. The levels of these three components are the desired level of the finished glove. It can be changed to obtain the desired properties. Remove the gloves from the tumble washer and partially Dry thoroughly, then turn inside out by hand. After that, let the gloves dry further. The gloves after processing should be dry. It can be easily put on with dry or wet hands.

[0091] (For chlorine treatment and lubrication processes, refer to U.S. 7,566 by reference) (See issue 6,502.) [Examples]

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

[0093] Vulcanization composition for synthetic polyisoprene

[0094] Examples 1-10 pertain to synthetic polyisoprene, and the composition of the compound is as follows: The base compounds shown in Table 1 and the accelerator compositions shown in Table 2 (represented by phr) Includes ( ). In Examples 1-8, the accelerator compositions (Table 2) are of various levels of DIXP (0.5 Combined with various levels of heptaldehyde-aniline (H) (0-5.00 phr), A) Includes (0.05~0.50 phr). Examples 9 and 10 contain DIXP or HA. However, not both. The gloves were formed using a standard solidifying agent immersion process and vulcanized using hot air. The characteristics of the gloves are shown in Table 4.

[0095] [Table 2]

[0096] Vulcanization composition for natural rubber polyisoprene

[0097] For examples 11-16 of natural rubber polyisoprene, the composition of the compound to be blended is shown in Table 1. It contains the base compound shown in [reference] and the accelerator composition shown in Table 3. The gloves are standard. The gloves were formed using a solidifying agent immersion process and vulcanized using hot air. The properties of the gloves are shown in Table 5. [Table 3]

[0098] Physical properties of polyisoprene gloves

[0099] Tensile strength

[0100] Tensile strength is measured according to ASTM D412 "Standard Test Methods for Vulcanized Rubber and Thermoplastic Elastomers". -Tensile (Standard Test Methods for Vulcanized Rubber and ThermoplasticElastomers-Tens Measured according to "ion". The ASTM standard for surgical gloves is ASTM D3577- 09. Defined in the standard specifications for rubber surgical gloves. That standard specifies natural rubber latex. This is classified as Type 1, and synthetic rubber latex as Type 2.

[0101] Physical properties of synthetic polyisoprene gloves

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

[0103] The tensile properties of molded gloves and chlorinated gloves (both unaged and aged) during latex maturation for 1 to 7 days are shown in Table 4. In eight accelerator compositions containing both DIXP and HA, molded (i.e., powdered) gloves and chlorinated (i.e., powder-free) gloves that meet the ASTM D3577 tensile strength requirements for aged and unaged synthetic rubber surgical gloves were obtained at aging times of 2 to 7 days. Unaged can be defined as "initial or current stage", or "not aged" or "before aging". Aged can be defined as "after aging". According to ASTM D3577 Standard - Section 8.5: Physical Requirements Testing, all surgical gloves must meet the physical requirements (before and after accelerated aging) specified in Table #3. The accelerated aging test is carried out in accordance with Test Method D573. The accelerated aging conditions are exposure at a temperature of 70°C ± 2°C for 166 hours ± 2 hours; 10

[0104] Unaged can be defined as "initial or current stage", or "not aged" or "before aging". Aged can be defined as "after aging". According to ASTM D3577 Standard - Section 8.5: Physical Requirements Testing, all surgical gloves must meet the physical requirements (before and after accelerated aging) specified in Table #3. The accelerated aging test is carried out in accordance with Test Method D573. The accelerated aging conditions are exposure at a temperature of 70°C ± 2°C for 166 hours ± 2 hours; 10 ent stage)", or "not aged" or "before aging". Aged can be defined as "after aging". According to ASTM D3577 Standard - Section 8.5: Physical Requirements Testing, all surgical gloves must meet the physical requirements (before and after accelerated aging) specified in Table #3. The accelerated aging test is carried out in accordance with Test Method D573. The accelerated aging conditions are exposure at a temperature of 70°C ± 2°C for 166 hours ± 2 hours; 10 aging". Aged can be defined as "after aging". According to ASTM D3577 Standard - Section 8.5: Physical Requirements Testing, all surgical gloves must meet the physical requirements (before and after accelerated aging) specified in Table #3. The accelerated aging test is carried out in accordance with Test Method D573. The accelerated aging conditions are exposure at a temperature of 70°C ± 2°C for 166 hours ± 2 hours; 10 aging". According to ASTM D3577 Standard - Section 8.5: Physical Requirements Testing, all surgical gloves must meet the physical requirements (before and after accelerated aging) specified in Table #3. The accelerated aging test is carried out in accordance with Test Method D573. The accelerated aging conditions are exposure at a temperature of 70°C ± 2°C for 166 hours ± 2 hours; 10 aging. According to ASTM D3577 Standard - Section 8.5: Physical Requirements Testing, all surgical gloves must meet the physical requirements (before and after accelerated aging) specified in Table #3. The accelerated aging test is carried out in accordance with Test Method D573. The accelerated aging conditions are exposure at a temperature of 70°C ± 2°C for 166 hours ± 2 hours; 10 aging. According to ASTM D3577 Standard - Section 8.5: Physical Requirements Testing, all surgical gloves must meet the physical requirements (before and after accelerated aging) specified in Table #3. The accelerated aging test is carried out in accordance with Test Method D573. The accelerated aging conditions are exposure at a temperature of 70°C ± 2°C for 166 hours ± 2 hours; 10 hours; 10 ​​​​It is after being exposed to a temperature of 0°C ± 2°C for 22 hours ± 0.3 hours.

[0105] For 1-day aging, except for Accelerator Composition 1, all of the other seven accelerator compositions were able to obtain molded gloves and chlorinated gloves that could meet the ASTM D3577 tensile strength requirements for both unaged and aged synthetic rubber surgical gloves. Examples 9 and 10 containing only DIXP or HA did not meet the tensile strength requirements.

[0106] . When not containing HA and using a high level of 5.0 phr of DIXP (Example 9), the unaged tensile strength (2 - 3 days of aging) was low (4.0 - 4.8 MPa) for molded gloves and 3.9 - 7.5 MPa for chlorinated gloves. When using a high level of 0.5 phr of HA and not using DIXP (Example 10), the unaged tensile strength (2 - 3 days of aging) was also low (0.4 MPa) for molded gloves and 0.4 - 1.3 MPa for chlorinated gloves. Therefore, accelerator compositions containing only DIXP or only HA give low tensile strength characteristics that cannot meet the requirements of ASTM D3577 for synthetic surgical gloves, even at high levels.

[0107] However, surprisingly, when combining 5.0 phr of DIXP with a very low level of 0.05 phr of HA (Example 1), the unaged tensile strength (2 - 3 days of aging) increased dramatically to 17.3 - 22.7 MPa for molded gloves and 22.4 - 24.7 MPa for chlorinated gloves. That is, these tensile properties meet the requirements of ASTM D3577 for synthetic surgical gloves. These results clearly show a strong synergistic effect between DIXP and HA.​​​​​​​​​​​​​It is shown there.

[0108] Furthermore, when using HA at a high level of 0.5 phr without DIXP (Example 10) ), the unaged tensile strength (after 2-3 days of maturation) is low (0.4 MPa) in molded gloves, and salt The pressure with untreated gloves was 0.4-1.3 MPa. However, surprisingly, it was 0.50 MPa. In the combination of hr HA and 0.50 phr low-level DIXP (Example 8), unaged The tensile strength (after 2-3 days of maturation) is 18.4-20.5 MPa for molded gloves and 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 before aging... The pressure is 24 MPa or higher, and 18 MPa or higher after accelerated aging. The composition of this invention is made from natural rubber. It was found to work very well with polyisoprene as well. In fact, the accelerator composition of the present invention As will be discussed in the following examples 11-16, these high values ​​for natural rubber polyisoprene The tensile strength specifications are lower levels of DIXP and HA (synthetic rubber polyisoprene). This can also be satisfied by comparison with [another method].

[0111] In Examples 11-16, the accelerator compositions (Table 3) were of various levels of HA (0.05-0.2 This includes combinations of 5 phr and various levels of DIXP (0.50-3.0 phr). nothing.

[0112] Table 5 shows the tensile strength characteristics of the films in Example 11-1.

Table 5

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

[0114] From Table 5, except for accelerator composition 15 (Example 15) in the 1-day aging of compounded latex, all accelerator compositions in the 1-day to 7-day aging of compounded latex can obtain gloves that meet the ASTM D3577 tensile strength specifications for natural rubber (polyisoprene) surgical gloves. This can be applied to both powdered (i.e., molded) samples and unpowdered (i.e., chlorinated) samples, and can also be applied before aging of the samples and after accelerated aging of the samples. after.

[0115] Residual DIXP

[0116] For samples of molded gloves from Example 1 (synthetic polyisoprene, 5.0 phr of DIXP, 0.05 phr of HA), Example 2 (synthetic polyisoprene, 3.0 phr of DIXP, 0.075 of HA) and Example 11 (natural rubber polyisoprene, 3.0 phr of DIXP, 0.05 phr of HA), residual DIXP was tested using UV spectroscopy and HPLC method. The molded gloves were extracted with spectroscopic grade hexane and the UV spectrum of the hexane extract was analyzed.

[0117] The results showed that there was no residual DIXP in the gloves molded from all three examples. .

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

[0119] These results confirmed that DIXP is indeed transient. Detection limits of both test methods. This is 1 ppm.

[0120] Of course, the above explanation is given merely as an example, and further details within the scope of the present invention will not be provided. It should be understood that corrections can be made.

[0121] This application cites various patents and publications. The full disclosure is provided by reference to more completely describe the state of the art to which this invention relates. This will be incorporated into this application.

[0122] As will be apparent to those skilled in the art who have the advantages of this disclosure, the present invention is comparative in form and function. Appropriate changes, modifications, and equivalents may be made.

[0123] Although the present invention has described what are currently considered preferred embodiments, the present invention is not limited to... The present invention is not limited to the spirit and scope of the detailed description above. It is intended to cover the various modifications and equivalent configurations included within.

[0124] The above description is intended to enable those skilled in the art to carry out the various embodiments described herein. It is provided for this purpose. Various modifications to these variations are readily apparent to those skilled in the art. The general principles defined herein can be applied to other embodiments. Various well-known examples described throughout this disclosure, which are publicly known or will become publicly known later. All structural and functional equivalents for the elements are expressly incorporated herein by reference. Born.

Claims

1. Sulfur source, At least one transient dihydrocarbyl xanthogen polysulfide enhancer, At least one aldehyde-aniline condensate, Metal oxides and, A vulcanizing composition containing the following:

2. The vulcanization composition according to claim 1, which does not contain a non-transient accelerator.

3. As a stimulant, dithiocarbamate, thiuram, thiazole, guanidine, or thiouria A vulcanizing composition according to claim 1, which does not contain any element.

4. A single transient dihydrocarbyl xanthogen polysulfide enhancer and a single It contains an aldehyde-aniline condensate, It does not contain additional compounds that act as accelerators for the vulcanization of elastomers. The vulcanizing composition according to claim 1.

5. The aforementioned sulfur source contains elemental sulfur, The at least one transient dihydrocarbyl xanthogen polysulfide promoter is Contains diisopropyl xanthogene polysulfide, The aforementioned at least one aldehyde-aniline condensate contains heptaldehyde-aniline Including, The aforementioned metal oxides are derived from zinc oxide, magnesium oxide, lead oxide, and combinations thereof. Selected from the following group, The vulcanizing composition according to claim 1.

6. The sulfur source is elemental sulfur and sulfur donor having low allergen potential, Then, a group is selected from the combinations of those groups, The at least one transient dihydrocarbyl xanthogen polysulfide promoter is Diisopropylxanthogen polysulfide (DIXP), diisopropylxanthogen Disulfide, diisopropyl xanthogent trisulfide, diisopropyl xanthogent Ntetrasulfide, diisopropylxanthogenpentasulfide, diisoamylxa Electrolyte trisulfide, diisoamyl tetrasulfide, diisoamyl tetrasulfide Santogenpentasulfide, diethylxanthogentetrasulfide, dibutylxane Togen tetrasulfide, dibutylxantogen disulfide, and combinations thereof Selected from the group consisting of, The vulcanizing composition according to claim 1.

7. The vulcanizing composition according to claim 1, which does not contain additional xanthogenic acid compounds.

8. The sulfur source is provided in an amount of approximately 0.5 to approximately 3 parts by dry weight per 100 parts by dry weight of rubber. Re, The at least one dihydrocarbyl xanthogen polysulfide promoter is rubber 1 It is provided in an amount of approximately 0.5 to approximately 5 parts by dry weight per dry parts by dry weight. The aforementioned at least one aldehyde-aniline condensate is present in a quantity of approximately 100 dry parts by weight of rubber. It is provided in the range of 0.05 to approximately 0.5 phr. The aforementioned metal oxide is present in a range of 0.1 to approximately 2 parts by dry weight per 100 parts by dry weight of rubber. To be provided, The vulcanizing composition according to claim 1.

9. The sulfur source is provided in an amount of approximately 1.0 to approximately 1.5 parts by dry weight per 100 parts by dry weight of rubber. Erected, The at least one dihydrocarbyl xanthogen polysulfide promoter is rubber 1 It is provided in an amount of approximately 1.0 to approximately 2.5 parts by dry weight per dry parts by dry weight. The aforementioned at least one aldehyde-aniline condensate is present in a quantity of approximately 100 dry parts by weight of rubber. It is provided in the range of 0.10 to approximately 0.25 phr. The metal oxide is present in an amount of 0.2 to approximately 0.8 parts by dry weight per 100 parts by dry weight of rubber. It is provided in an enclosure. The vulcanizing composition according to claim 8.

10. An elastomer article formed using the vulcanizing composition described in claim 1, wherein the composition The material is an elastomer article that does not contain non-transient accelerators.

11. The elastomer article according to claim 10, wherein the elastomer article contains less than 1 ppm of residual DIXP. Stomatous goods.

12. An elastomer article formed using the vulcanization composition described in claim 7, wherein the elastomer Elastomer articles that do not contain additional compounds that function as accelerators for vulcanization of the mer. 。

13. The elastomer articles include gloves, probe covers, finger cots, catheters, and dental dams. The elastomer article according to claim 12, selected from the group consisting of and condoms.

14. The elastomer article according to claim 12, wherein the elastomer article is powder-free.

15. Elemental sulfur, Diisopropyl xanthogene polysulfide and Heptaldehyde-aniline and, Metal oxides and, A vulcanizing composition consisting of the following.

16. Polyisoprene and, Elemental sulfur, diisopropyl xanthogene polysulfide, heptaldehyde-aniline and a vulcanizing composition consisting of a metal oxide, A latex dispersion containing the above.

17. Claims that the following compounds are not included, which function as accelerators for vulcanizing elastomers. The latex dispersion described in 16.

18. How to prepare polyisoprene elastomer articles with reduced allergen potential. It is a law, A step of providing the latex dispersion according to claim 16, The molding tool is coated with the latex dispersion by immersion in a coagulant to form the first elastomer layer. The process to be completed, The process involves drying and vulcanizing the first elastomer layer, Methods that include...

19. The molding tool coated with the first elastomer layer is then coated with the second latex dispersion. The process further includes the step of forming a second elastomer layer, The second elastomer layer is suitable before drying and vulcanizing the first elastomer layer. to be used The method according to claim 18.

20. The claim that the second elastomer layer has the same composition as the first elastomer layer. The method described in 19.

21. The second elastomer layer has a different composition from the first elastomer layer. The method described in item 19.

22. The second elastomer layer is made of natural rubber, polyurethane, polybutadiene, and polychloro Preene, nitrile rubber, styrene and butadiene block copolymer, styrene and isop A second selected from the group consisting of len block copolymers and synthetic polyisoprene The latex dispersion according to claim 19, which is formed from a latex dispersion further comprising polymer latex. method.

23. A coating composition for elastomer articles, The latex dispersion according to claim 16, Natural rubber, polyurethane, polybutadiene, polychloroprene, nitrile rubber, styrene Block copolymer of styrene and butadiene, block copolymer of styrene and isoprene, A second polymer latex selected from the group consisting of and synthetic polyisoprene, Water and, Includes, The total solids content of the coating composition is approximately 3% to approximately 15%. Coating composition for elastomer articles.

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

25. An elastomer article formed using the latex dispersion described in claim 16, Elastomers without additional compounds that act as accelerators for vulcanization. Mar goods.

26. An elastomer article formed using the coating composition described in claim 23, Elastomers do not contain additional compounds that act as accelerators for vulcanization. tomer goods.

27. The elastomer articles include gloves, probe covers, finger cots, catheters, and dental dams. Selected from the group consisting of, and condoms, The aforementioned elastomer article is powder-free. The elastomer article according to claim 25.

28. The elastomer articles include gloves, probe covers, finger cots, catheters, and dental dams. Selected from the group consisting of, and condoms, The aforementioned elastomer article is powder-free. The elastomer article according to claim 26.

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