JP2007501144A - Elastomeric articles that are easy to wear - Google Patents

Abstract

An elastomeric article that is easy to wear, such as a glove or a condom, and a method of forming such an article.
An elastomeric article comprising a substrate (26) having a first surface (28). The substrate (26) is formed from an elastomeric material. The wear layer (32) overlies at least a portion of the first surface (28). The wear layer (32) is formed from a styrene block copolymer.
[Selection] Figure 2A

Description

Highly elastic articles such as surgical and examination gloves have traditionally been formed from natural rubber latex due to their good elasticity and strength combination. In recent years, synthetic gloves having comparable properties have been introduced for such applications. One such glove is that formed from a styrene-ethylene-butylene-styrene (S-EB-S) synthetic block copolymer.
Elastomeric articles having a close fit can be difficult to wear, whether made of natural or synthetic polymers. To overcome this problem, it is conventional practice to add a powder lubricant to a surface that contacts the user's body, such as the inside of a glove. However, the presence of such powders may not be desirable in certain situations, such as surgical procedures. Thus, there is a need for synthetic gloves that are easily worn without the use of powder.

The present invention generally relates to elastomeric articles that are easy to wear, such as gloves or condoms, and methods of forming such articles.
The present invention relates to an elastomeric article comprising a substrate formed from an elastomeric material and having a first surface, and a wear layer overlying at least a portion of the first surface. The wear layer can be formed from a styrene block copolymer. The elastomeric material can comprise an intermediate block saturated styrene block copolymer, such as a styrene-ethylene-butylene-styrene block copolymer. The styrene block copolymer used to form the wear layer can include a styrene-butadiene-styrene block copolymer. The article can further include a lubricating layer overlying at least a portion of the wear layer.

  The present invention further includes a substrate formed from an elastomeric material and having a first surface and a second surface, and a wear layer formed from a styrene-butadiene-styrene block copolymer and overlying at least a portion of the first surface. And a grip layer overlying at least a portion of the second surface of the substrate. In some cases, the elastomeric material can include an intermediate block saturated styrene block copolymer such as a styrene-ethylene-butylene-styrene block copolymer. In some cases, the grip layer can be formed from a styrene-butadiene-styrene block copolymer. The article can further include a lubricating layer overlying at least a portion of the wear layer.

  The invention also relates to a method of preparing an elastomeric article. The method can include forming a substrate having a first surface and a second surface from an elastomeric material and overlying at least a portion of the first surface and formed from a styrene-butadiene-styrene block copolymer. Forming a wear layer. The method envisions forming a grip layer that can be formed from a styrene-butadiene-styrene block copolymer on at least a portion of the second surface of the substrate. In some cases, the grip layer can be contacted with a chlorine source. The method further envisages forming a lubricating layer that can include silicone on at least a portion of the wear layer.

(Description of the invention)
The present invention generally relates to elastomeric articles such as condoms or gloves, and methods of forming such elastomeric articles. As used herein, the term “elastomeric article” means an article formed primarily from an elastomeric material. As used herein, the term “elastomeric material” refers to a polymeric material that can be easily stretched or expanded, and that upon release of the stretching or expansion force, will substantially return to its original shape. means.

  Articles made according to the present invention are characterized by improved wear characteristics that do not use powder. An article, such as a glove 20, generally includes an inner surface 22 and an outer surface 24 (FIG. 1). As used herein, the term “inner surface” means the surface of an article that contacts the wearer's body. As used herein, the term “outer surface” means the surface of an article distal to the wearer's body. The glove includes a substrate 26 having a first surface 28 and a second surface 30 (FIGS. 2A-2C). As used herein, the term “first surface” means the surface of a substrate proximal to the wearer's body. As used herein, the term “second surface” means the surface of the substrate distal from the wearer's body.

  The articles of the present invention can include single or multiple layers as desired. In a single-layer glove that includes only a substrate, the first surface can form the inner surface of the glove. However, in a multi-layer glove having an additional layer proximal to the wearer's body, the one or more additional layers can each form a portion of the inner surface or the entire inner surface as desired. . Similarly, in a single-layer glove that includes only a substrate, the second surface can form the outer surface of the glove. However, in a multi-layer glove having an additional layer distal from the wearer's body, the one or more additional layers can each form a portion of the outer surface or the entire outer surface as desired. .

  For example, as shown in FIG. 2A, the article can include a wear layer 32 overlying at least a portion of the first surface 28 of the substrate 26. In such an article, the wear layer 32 forms at least a portion of the inner surface 22 of the glove 20. As shown in FIG. 2B, the article 20 can also include a grip layer 34 overlying at least a portion of the second surface 30 of the substrate 26. In such articles, the grip layer 34 forms at least a portion of the outer surface 24 of the glove 20. As shown in FIG. 2C, the article can also include other layers, such as a lubricating layer 36 overlying at least a portion of the wear layer 32. In such an article, the lubricating layer 36 forms at least a portion of the inner surface 22 of the glove 20.

  The substrate 26 (FIGS. 2A-2C) can be formed from an elastomeric material, and in some embodiments, the substrate can be formed from an intermediate block saturated styrene block copolymer. For example, the substrate can be formed from a styrene-ethylene-butylene-styrene (S-EB-S) block copolymer. In other embodiments, the substrate can be formed from two or more elastomeric materials. For example, the substrate is described in US Pat. Nos. 5,112,900 and 5,407,715 to Buddenhagen et al., Both of which are hereby incorporated by reference in their entirety. It can be formed from two or more S-EB-S block copolymers such as those. Examples of S-EB-S polymers that may be suitable for use in the present invention are Clayton Polymers (Houston, Texas, USA) under the trade designations “KRATON® 1650” and “KRATON® 1651”. ) To commercially available products. “KRATON® 1650” is believed to contain 30% by weight of block styrene. “KRATON® 1651” is believed to contain 33% by weight of block styrene.

  While articles formed from S-EB-S are described in detail herein, it should be understood that any other suitable polymer or combination of polymers can be used in the present invention. For example, in another embodiment, the elastomeric material can include natural rubber, which can generally be provided as natural rubber latex. In yet another embodiment, the elastomeric material can include nitrile butadiene rubber, and in particular can include carboxylated nitrile butadiene rubber. In other embodiments, the elastomeric material is a styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene block copolymer, styrene-butadiene block copolymer, synthetic isoprene, chloroprene rubber, polyvinyl chloride, silicone rubber, Or a combination thereof.

  The wear layer 32 (FIGS. 2A-2C) can be formed from any polymer that facilitates wear of the article, and in some embodiments can include a block copolymer. One such polymer that may be suitable for use in the present invention is a styrene block copolymer. In one embodiment, the wear layer can be formed from a styrene-butadiene-styrene (SBS) block copolymer. One example of an SBS polymer that may be suitable for use as a wear layer is commercially available from Dexco Polymers (Houston, Texas, USA) under the trademark “VECTOR® 8508”. “VECTOR® 8508” is believed to be a linear pure triblock copolymer (containing less than 1% diblock copolymer) produced using anionic polymerization. Another example of an SBS polymer that may be suitable for use as a wear layer is also commercially available from Dexco Polymers (Houston, Texas, USA) under the trademark "VECTOR (R) 8550".

  In another embodiment, unsaturated styrene-isoprene (SIS) with triblocks or radial blocks can be used. In some cases, the SIS block copolymer can have a polystyrene endblock content of about 10% to about 20% by weight of the total weight of the SIS block copolymer. In another embodiment, the SIS block copolymer can have a polystyrene endblock content of about 15% to about 18% by weight of the total weight of the SIS block copolymer. Further, the molecular weight of the polystyrene endblock can be at least about 5000 grams / mole. Some examples of suitable intermediate block unsaturated SIS block copolymers include, but are not limited to, “KRATON® D1107” available from Clayton Polymers (Houston, Texas, USA), and Dexco Includes “VECTOR® 511” and “VECTOR® 4111” available from Polymers (Houston, Texas, USA).

  The article can also include a grip layer (FIGS. 2B-2C) overlying the second surface 30 of the substrate 26. The grip layer can be formed from any polymer, and in some embodiments, the grip layer can be formed from an unsaturated elastomeric polymer capable of chlorination. For example, the grip layer can be formed from a styrene-butadiene-styrene block copolymer. One example of an SBS polymer that may be suitable for use as a gripping layer is commercially available from Dexco Polymers (Houston, Texas, USA) under the trade name “VECTOR® 8508” as detailed above. Yes. Another example of an SBS polymer that may be suitable for use as a gripping layer is also commercially available from Dexco Polymers (Houston, Texas, USA) under the trade designation “VECTOR® 8550”.

  The article can also include a lubricating layer 36 (FIG. 2C) overlying at least a portion of the wear layer to further facilitate wear. In one embodiment, the lubricating layer can contain silicone or silicone-based components. As used herein, the term “silicone” includes, but is not limited to, the group consisting of amino, carboxyl, hydroxyl, ether, polyether, aldehyde, ketone, amide, ester, and thiol groups. Generally refers to a broad family of synthetic polymers having a repetitive silicon-oxygen backbone, including polydimethylsiloxanes and polysiloxanes having hydrogen-bonded functional groups selected from In some embodiments, polydimethylsiloxane and / or modified polysiloxane can be used as the silicone component according to the present invention. For example, some suitable modified polysiloxanes that can be used in the present invention include, but are not limited to, phenyl modified polysiloxanes, vinyl modified polysiloxanes, methyl modified polysiloxanes, fluoro modified polysiloxanes, Including alkyl-modified polysiloxanes, alkoxy-modified polysiloxanes, amino-modified polysiloxanes, and combinations thereof.

  In some embodiments, the lubricating layer can include a silicone emulsion. One such silicone emulsion that may be suitable for use in the present invention is "DC 365", a pre-emulsified silicone (35% TSC) commercially available from Dow Corning Corporation (Midland, Michigan, USA). . “DC 365” is 40-70 wt% water, 30-60 wt% methyl modified polydimethylsiloxane, 1-5 wt% propylene glycol, 1-5 wt% polyethylene glycol sorbitan monolaurate, and 1-5 wt% It is believed to contain octylphenoxy polyethoxyethanol. Another silicone emulsion that may be suitable for use in the present invention is "SM 2140", commercially available from GE Silicones (Waterford, NY, USA). “SM 2140” is 30-60 wt% water, 30-60 wt% amino modified polydimethylsiloxane, 1-5 wt% ethoxylated nonylphenol, 1-5 wt% trimethyl-4-nonyloxypolyethyleneoxyethanol, and small It is a pre-emulsified silicone (50% TSC) that is believed to contain proportions of acetaldehyde, formaldehyde, and 1,4 dioxane. Another silicone emulsion that may be suitable for use in the present invention is "SM 2169" available from GE Silicones (Waterford, NY, USA). “SM 2169” is a pre-emulsified silicone believed to contain 30-60 wt% water, 60-80 wt% polydimethylsiloxane, 1-5 wt% polyoxyethylene lauryl ether, and a small amount of formaldehyde. . Yet another silicone that may be suitable for use in the present invention is commercially available from GE Silicones (Waterford, NY, USA) under the trademark "AF-60". “AF-60” is believed to contain polydimethylsiloxane, acetaldehyde, and a small proportion of emulsifier. If desired, these pre-emulsified silicones can be diluted with water or other solvents prior to use.

In another embodiment, the lubricating layer may contain a quaternary ammonium compound, such as that commercially available under the trade designation “VERISOFT® BTMS” from Goldschmidt Chemical Corporation, Dublin, Ohio. . “VERISOFT® BTMS” is believed to contain benyltrimethyl sulfate and cetyl alcohol. Thus, for example, in one embodiment, the lubricating layer comprises a quaternary ammonium compound such as “VERISOFT® BTMS” and a silicone emulsion such as “SM 2169”.
In other embodiments, the lubricating layer may include, for example, a cationic surfactant (eg, cetylpyridinium chloride), an anionic surfactant (eg, sodium lauryl sulfate), or a nonionic surfactant. it can.

  In some embodiments, one or more cationic surfactants can be used. Examples of cationic surfactants that may be suitable for use in the present invention include, for example, behenetrimonium methosulfate, distearyl dimonium chloride, dimethyl dioctadecyl ammonium chloride, cetyl pyridinium chloride, methyl benzethonium chloride, hexa Decylpyridinium chloride, hexadecyltrimethylammonium chloride, benzalkonium chloride, dodecylpyridinium chloride, its corresponding bromide, hydroxyethylheptadecylimidazolium halide, cocoaminopropyl betaine, and coconut alkyldimethylammonium betaine. Additional cationic surfactants that can be used are methylbis (hydrogenated tallowamidoethyl) -2-hydroxyethylammonium methylsulfate, methylbis (tallowamidoamidoethyl) -2-hydroxyethylammonium methylsulfate, methylbis (soyamidoethyl)- 2-hydroxyethylammonium methylsulfate, methylbis (rapeseed amideethyl) -2-hydroxyethylammonium methylsulfate, methylbis (tallowamidoethyl) -2-tallow imidazolinium methylsulfate, methylbis (hydrogenated tallowamidoamidoethyl) -2-hydrogenated tallow Imidazolinium methyl sulfate, methylbis (ethyl beef tallow fatty acid) -2-hydroxyethylammonium methyl sulfate, dihydrogenated tallow dimethylammoni Including Mukurorido, didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, octyl decyl dimethyl ammonium chloride, di amidoamine ethoxylates, diamide amine imidazolines, and quaternary ester salts.

In some embodiments, one or more nonionic surfactants can be used. Nonionic surfactants are generally hydrophilic containing a hydrophobic base, such as a long chain alkyl group or an alkylated allyl group, and a certain number (eg, 1 to about 30) of ethoxy and / or propoxy moieties. Having a sex chain. Examples of some classes of nonionic surfactants that can be used include, but are not limited to, ethoxylated alkylphenols, ethoxylated and propoxylated fatty alcohols, polyethylene glycol ethers of methyl glucose, sorbitol polyethylene glycol ethers of ethylene oxide - propylene oxide block copolymers, fatty (C ₈ -C ₁₈₎ ethoxylated esters of acids, condensation products of ethylene oxide by the long chain amines or amides, condensation products of ethylene oxide with an alcohol, and mixtures thereof including.

Specific examples of suitable nonionic surfactants include, but are not limited to, methylgluces-10, PEG-20 • methylglucose distearate, PEG-20 • methylglucose sesquistearate, C _{11− 15} palace-20, ceteth-8, ceteth-12, dodoxynol-12, laureth-15, PEG-20, castor oil, polysorbate 20, steareth-20, polyoxyethylene-10 cetyl ether, polyoxyethylene-10. Stearyl ether, polyoxyethylene-20 cetyl ether, polyoxyethylene-10 oleyl ether, polyoxyethylene-20 oleyl ether, ethoxylated nonylphenol containing 3 to 20 ethylene oxide moieties, ethoxylated octylphenol, ethoxy Le of dodecylphenol, or ethoxylated fatty (C ₆ -C ₂₂₎ alcohols, polyoxyethylene -20-isohexadecyl ether, polyoxyethylene -23-glycerol monolaurate, polyoxy - ethylene -20-glyceryl stearate, PPG -10 · methyl glucose ether, PPG-20 · methyl glucose ether, polyoxyethylene-20 · sorbitan monoester, polyoxyethylene-80 · caster oil, polyoxyethylene-15 · tridecyl ether, polyoxy-ethylene-6 · Tridecyl ether, laureth-2, laureth-3, laureth-4, PEG-3 castor oil, PEG600 dioleoate, PEG400 dioleoate, oxyethanol, 2,6,8-trimethyl-4- Nyloxypolyethyleneoxyethanol, octylphenoxypolyethoxyethanol, nonylphenoxypolyethoxyethanol, 2,6,8-trimethyl-4-nonyloxypolyethylenealkyleneoxypolyethyleneoxyethanol, alkyleneoxypolyethyleneoxyethanol, alkyleneoxypolyethyleneoxyethanol, and Including mixtures thereof.

Additional nonionic surfactants that can be used are secondary aliphatic alcohols containing from about 8 to about 18 carbon atoms in a linear or branched structure condensed with about 5 to about 30 moles of ethylene oxide. A water-soluble alcohol ethylene oxide condensate which is a condensation product of Such nonionic surfactants are commercially available from Union Carbide Corporation (Danbury, Conn., USA) under the trade name “TERGITL®”. A specific example of such a commercially available nonionic surfactant of the type described above is 9 moles of ethylene oxide (TERGITL® 15-S— sold by Union Carbide Corporation (Danbury, Conn., USA). C ₁₁ -C ₁₅ secondary alkanol condensed with either 9) or 12 moles of ethylene oxide (TERGITL® 15-S-12).

  Other suitable nonionic surfactants are polyethylene oxide condensates of 1 mole of alkylphenol containing from about 8 to about 18 carbon atoms in a linear or branched alkyl group having from about 5 to about 30 moles of ethylene oxide. including. Specific examples of alkylphenol ethoxylates include nonyl condensed with about 9.5 moles of ethylene oxide per mole of nonylphenol, dinonylphenol condensed with about 12 moles of ethylene oxide per mole of phenol, about 15 moles of ethylene oxide per mole of phenol. Condensed dinonylphenol and diisooctylphenol condensed with about 15 moles of ethylene oxide per mole of phenol. Commercially available nonionic surfactants of this type include “IGEPAL® CO-630” (nonylphenol ethoxylate) sold by ISP Corporation (Wayne, NJ, USA). Suitable nonionic ethoxylated octyl and nonylphenols include those having from about 7 to about 13 ethoxy units.

  In some embodiments, one or more amphoteric surfactants can be used. One class of amphoteric surfactants that may be suitable for use in the present invention includes secondary amines or tertiary amine derivatives having aliphatic radicals that are linear or branched, and are suitable for aliphatic substituents. One contains about 8 to 18 carbon atoms and the at least one aliphatic substituent contains an anionic water-soluble group such as, for example, a carboxy, sulfonate, or sulfate group. Some examples of amphoteric surfactants include, but are not limited to, sodium 3- (dodecylamino) propionate, sodium 3- (dodecylamino) -propane-1-sulfonate, sodium 2- (dodecylamino) ) Ethyl sulfate, sodium 2- (dimethylamino) octadecanoate, disodium 3- (N-carboxymethyl-dodecylamino) propane-1-sulfonate, sodium 1-carboxymethyl-2-undecylimidazole, disodium octadecyl Iminodiacetate, and sodium N, N-bis (2-hydroxyethyl) -2-sulfato-3-dodecoxypropylamine.

  Additional classes of suitable amphoteric surfactants include phosphobetaines and phosphitaines. For example, some examples of such amphoteric surfactants include, but are not limited to, sodium coconut N-methyl taurate, sodium oleyl N-methyl taurate, sodium tall oil N-methyl Taurate, cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethylcarboxyethylbetaine, cetyldimethylcarboxymethylbetaine, sodium palmitoyl N-methyltaurate, oleyldimethylgammacarboxypropylbetaine, lauryl-bis- (2- Hydroxypropyl) -carboxyethylbetaine, disodium oleamide / PEG-2 / sulfosuccinate, laurylamide-bis- (2-hydroxyethyl) propylsultain, lauryl-bis- (2-hi Roxyethyl) carboxymethyl betaine, cocoamidodimethylpropyl sultain, stearylamide dimethylpropyl sultain, TEA / oleamide / PEG-2 / sulfosuccinate, disodium oleamide / MEA / sulfosuccinate, disodium oleamide / MIPA Sulfosuccinate, disodium ricinolamide / MEA / sulfosuccinate, disodium undecylenamide / MEA / sulfosuccinate, disodium wheat germamide / MEA / sulfosuccinate, disodium wheat germamide / PEG-2 / sulfosuccinate, disodium Isostearamide, MEA, sulfosuccinate, cocoamidopropyl monosodium phosphiteine, laurin myristinamidopropyl monosodium phosphita Cocoamido disodium 3-hydroxypropyl phosphobetaine, laurin myristin amide disodium 3-hydroxypropyl phosphobetaine, laurin myristic amide glyceryl phosphobetaine, laurin myristinamide carboxydisodium 3-hydroxypropyl phosphobetaine, coco amphoglycinate , Cocoamphocarboxyglycinate, capryloamphocarboxyglycinate, lauroamphocarboxyglycinate, lauroamphoglycinate, capryloamphocarboxypropionate, lauroamphocarboxypropionate, cocoamphopropionate, Cocoamphocarboxypropionate, dihydroxyethyl tallow glycinate, and mixtures thereof.

  In certain cases, one or more anionic surfactants can be used. Suitable anionic surfactants include, but are not limited to, alkyl sulfates, alkyl ether sulfates, alkyl ether sulfonates, sulfate esters of alkylphenoxypolyoxyethylene ethanol, alpha olefin sulfonates, beta alkoxy alkane sulfonates, alkyls Lauryl sulfonate, alkyl monoglyceride sulfate, alkyl monoglyceride sulfonate, alkyl carbonate, alkyl ether carboxylate, fatty acid, sulfosuccinate, sarcosinate, octoxynol or nonoxynol phosphate, taurate, fatty tauride, fatty acid amide polyoxyethylene sulfate, isethionate Or a mixture thereof.

Specific examples of some suitable anionic surfactants include, but are not limited to, C ₈ -C ₁₈ alkyl sulfates, C ₈ -C ₁₈ fatty acid salts, 1 or 2 moles of ethoxylation. C ₈ -C ₁₈ alkyl ether sulfates, C ₈ -C ₁₈ alkamines oxide, C ₈ -C ₁₈ alkoyl sarcosinates, C ₈ -C ₁₈ sulfoacetate, C ₈ -C ₁₈ sulfosuccinates, C ₈ having - C ₁₈ alkyl diphenyl oxide disulfonates, including C ₈ -C ₁₈ alkyl carbonate, C ₈ -C ₁₈ alpha olefin sulfonates, methyl ester sulfonates, and blends thereof. C ₈ -C ₁₈ alkyl group, straight chain (e.g., lauryl) or branched (e.g., 2-ethylhexyl) can be. Cation of the anionic surfactant, alkali metal (e.g., sodium or potassium), ammonium, C ₁ -C ₄ alkyl ammonium (e.g., mono-, - di -, tri), or C ₁ -C ₃ alkanolammonium ( For example, mono-, di-, tri).

Specific examples of such anionic surfactants include, but are not limited to, lauryl sulfate, octyl sulfate, 2-ethylhexyl sulfate, lauramine oxide, decyl sulfate, tridecyl sulfate, cocoate, lauroyl sulfate Koshineto, lauryl sulfosuccinates, linear C ₁₀ diphenyl oxide disulfonates, lauryl sulfosuccinates, lauryl ether sulfates (1 and 2 moles ethylene oxide), myristyl sulfates, oleates, stearates, tallates, ricinoleates And cetyl sulfate.

  The articles of the present invention can be formed using various processes such as, for example, dipping, spraying, spinning, drying, and curing. Although a typical dipping process for forming a glove is described herein, other processes can be used to form a variety of articles having different shapes and characteristics. For example, condoms can be formed in substantially the same manner, but some processing conditions may differ from those used to form the gloves. Further, it should be understood that batch processing, semi-batch processing, or continuous processing can be used with the present invention.

The glove is formed with a hand-shaped mold called a “forming mold”. The mold can be made from any suitable material such as, for example, glass, metal, or porcelain. The forming surface forms at least a portion of the surface of the glove to be manufactured.
In general, the substrate 26 (FIGS. 1-2C) is formed by dipping a forming mold in a series of compositions as needed to achieve the desired glove characteristics. The glove can be solidified between the layers. It should be understood that any combination of layers can be used, and specific layers are described herein, but other layers and combinations of layers can be used as desired.

  In one embodiment, the substrate can be formed using a solvent-based dipping process. Exemplary processes are described in U.S. Pat. No. 5,112,900 to Badenhagen et al., U.S. Pat. No. 5,407,715 and U.S. Pat. No. 5,792,531 to Littleton et al., Which are described briefly below. For example, in such a process, the S-EB-S block copolymer is dissolved in a solvent, such as toluene, and then mixed with a plasticizer. The glove forming mold is then immersed in the solution and dried to evaporate the solvent. Several dippings can be used as needed to create the desired thickness. The finished article can be rinsed or otherwise processed as needed.

  In another embodiment, the glove can be formed using an aqueous dispersion based dipping process. Exemplary processes are described in US Pat. No. 5,900,452 to Plumsottam and US Pat. No. 6,414,083 to Plumsottam, both of which are hereby incorporated by reference in their entirety. It is described here and will be briefly described below. For example, a dispersion medium is prepared from water and a surfactant. Other additives such as thickeners, antifoams, or buffers can be added to the dispersion medium. Alternatively, a mixture of S-EB-S block copolymer, solvent, and mineral oil plasticizer is prepared. The two mixtures are then combined under high shear conditions to form the desired dispersant. The solvent is then removed from the dispersant through a suitable stripping process. Next, the elastomeric article is formed by immersing the forming mold one or more times in a certain amount of dispersant to create the desired thickness and then evaporating the water to form a film on the surface of the forming mold. It is formed. The finished article can be rinsed or otherwise processed as needed.

  After formation of the substrate 26, the mold can be dipped into a composition containing a suitable polymeric material to coat the first surface 28 of the substrate 26. Such a coating forms a wear layer 32 (FIGS. 2A-2C) and facilitates wearing of the finished article, ie, the glove 20. In one embodiment, the wear layer can include an SBS block copolymer. One example of an SBS polymer that may be suitable for use as a wear layer is commercially available from Dexco Polymers (Houston, Texas, USA) under the trade name “VECTOR® 8508” as detailed above. Yes. In some embodiments, the wear layer composition can include about 1 wt.% To about 10 wt.% SBS in a suitable solvent such as toluene. In another embodiment, the wear layer composition can include from about 2 wt% to about 5 wt% SBS in a suitable solvent. In yet another embodiment, the wear layer composition can include about 3% to about 4% by weight of SBS in a suitable solvent. In yet another embodiment, the wear layer composition can include about 3.4% by weight SBS in a suitable solvent. While typical compositions are presented herein, it should be understood that the wear layer can be formed using any suitable amount of other polymers as described herein.

  That is, for example, the articles of the present invention can include a substrate 26 and a wear layer 32 (FIG. 2A), which can be formed from one or more S-EB-S block copolymers, and the wear layer 32. Can be formed from SBS block copolymers. The wear layer may be present in any suitable amount, and in some embodiments the wear layer may be present in an amount from about 0.1% to about 2.5% by weight of the elastomeric article. it can. In other embodiments, the wear layer can be present in an amount from about 0.25% to about 1.5% by weight of the elastomeric article. In yet other embodiments, the wear layer can be present in an amount of about 0.5% by weight of the elastomeric article.

  If grip layer 34 (FIGS. 2B-2C) is desired, the mold can be dipped into a composition containing a suitable polymer material prior to formation of substrate 26. The grip layer allows the wearer to securely grasp the article without excessive stickiness and viscosity. In one embodiment, the grip layer can include an SBS block copolymer. One example of an SBS polymer that may be suitable for use as a gripping layer is commercially available from Dexco Polymers (Houston, Texas, USA) under the trade name “VECTOR® 8508” as detailed above. Yes. In one embodiment, the grip layer composition can include from about 1 wt% to about 10 wt% SBS in a suitable solvent such as toluene. In another embodiment, the grip layer composition can include from about 2% to about 5% by weight SBS in a suitable solvent. In yet another embodiment, the grip layer composition can comprise from about 3 wt% SBS to about 4 wt% SBS in a suitable solvent. In yet another embodiment, the grip layer composition can include about 3.4% by weight SBS in a suitable solvent. While typical compositions are presented herein, it should be understood that any amount of other polymers can be used to form the grip layer as described herein.

  That is, for example, the articles of the present invention can include a substrate and a grip layer, wherein the substrate is formed from one or more S-EB-S block copolymers, and the grip layer is formed from an SBS block copolymer. In another example shown in FIG. 2B, an article of the invention can include a substrate 26, a wear layer 32, and a grip layer 34, the substrate 26 being formed from one or more S-EB-S block copolymers. The wear layer 32 can be formed from an SBS block copolymer and the grip layer 34 can be formed from an SBS block copolymer. The grip layer may be present in any suitable amount, and in some embodiments the grip layer may be present in an amount from about 0.1% to about 2.5% by weight of the elastomeric article. it can. In other embodiments, the grip layer may be present in an amount from about 0.25% to about 1.5% by weight of the elastomeric article. In yet other embodiments, the grip layer can be present in an amount of about 0.5% by weight of the elastomeric article.

Once all the desired polymer layers have been formed and the glove has solidified, the mold can be transferred to a stripping station that removes the glove from the mold. The stripping station will involve automatic or manual removal of the glove from the mold. For example, in one embodiment, the glove is manually removed and turned inside out as it is peeled from the mold.
The solidified glove can then be subjected to various post-forming steps. In some cases, the glove can be inverted as necessary to expose the wear layer and / or the grip layer for halogenation. Halogenation (eg chlorination) can be carried out in any suitable manner known to those skilled in the art. Chlorination generally requires contacting the surface to be chlorinated with a chlorine source. Such methods include (1) direct injection of chlorine gas into the water mixture, (2) mixing high density bleaching powder and aluminum chloride in water, (3) salt electrolysis to produce chlorine water, And (4) acidified bleaching. Examples of such methods are U.S. Pat. No. 3,411,982 to Kavalir, 3,740,262 to Agostinelli, the entire contents of which are incorporated herein by reference. No. 3,992,221 granted to Hornsey et al., No. 4,597,108 granted to Momose, No. 4,851,266 granted to Momose, and No. 5 granted to Littleton et al. 792,531. In one embodiment, for example, chlorine gas is injected into a stream of water and then delivered into a chlorinator (closed container) containing gloves. The degree of chlorination can be controlled by changing the concentration of chlorine. The chlorine concentration is typically at least about 100 parts per million (ppm), in some embodiments from about 200 ppm to about 3500 ppm, and in some embodiments from about 300 ppm to about 600 ppm, such as about 400 ppm. The duration of the chlorination stage can be controlled to vary the degree of chlorination, for example in the range of about 1 to about 10 minutes, for example 4 minutes.

When still in the chlorinator, the chlorinated gloves can then be rinsed with tap water at about room temperature. This rinse cycle can be repeated as needed. With all the water removed, turn over the gloves and drain the excess water.
If desired, the lubricating composition can then be added into the chlorinator over about 5 minutes. The lubricant forms the lubricant layer 36 on at least a part of the wear layer 32, and further improves the wearability of the glove 20 (FIG. 2C). As shown herein, any suitable lubricant can be used to form the lubricating layer. One such lubricant may comprise a quaternary ammonium compound such as “VERISOFT® BTMS” and a silicone emulsion such as “SM 2169”, both as described in detail above.

The lubricating solution is then drained from the chlorinator and can be reused as needed. It should be understood that the lubricating composition can be applied at a later stage of the forming process and can be applied using any technique such as dipping, spraying, dipping, printing, or rotating. is there.
The coated glove is then placed in a dryer and dried at about 20 ° C. to 80 ° C. (eg, 40 ° C.) for about 10 to about 60 minutes (eg, 40 minutes) to dry the inner surface of the glove. Next, the glove 20 is inverted and the outer surface of the glove is dried at about 20 ° C. to 80 ° C. (eg, 40 ° C.) for about 20 to about 100 minutes (eg, 60 minutes).
These findings are demonstrated in the following examples that are not intended to be limiting in any case.

  The function of wearing and using an article formed according to the present invention has been clarified. To form the grip layer, hundreds of glove forming molds are available from about 3 of the “VECTOR® 8508” styrene-butadiene-styrene (SBS) block copolymer available from Dexco Polymers (Houston, Texas, USA). It was immersed in a 4% by mass toluene solution. Thereafter, the glove forming mold was exposed to air to evaporate the solvent.

The glove forming mold then has “KRATON® 1650” and “KRATON® 1651” (67 parts per hundred rubber (phr) by mass of mineral oil) to form the substrate. ) And an equivalent amount of 20.7 mass% toluene solution. The solution was mixed with a high shear mixer equipped with a cowl blade. After immersing the forming mold in the solution, the glove forming mold was exposed to air and most of the solvent was allowed to evaporate. The glove former was then dipped a second time in the same solution, and the former was subsequently exposed to air to evaporate most of the solvent.
The forming mold was then dipped again in a toluene solution of “VECTOR 8508®” SBS block copolymer (approximately 3.4 wt% SBS) to form a wear layer. The mold was then exposed to air to evaporate the solvent.

The glove bead was then stretched over the glove by bringing the rotating forming mold into contact with two opposing rotating brushes.
The mold was then dipped in a slurry solution containing calcium carbonate and surfactant to facilitate glove release. The mold was then again exposed to air to remove water from the slurry and the remaining toluene solvent. The gloves were then peeled off from the mold manually.

  The gloves were then exposed to a solution of water, chlorine gas, and sufficient hydrochloric acid for about 7 minutes to produce a pH 2 solution. The gloves were then inverted and exposed to another solution of water, chlorine gas, and hydrochloric acid. The gloves were then coated with an aqueous lubricating composition containing a quaternary ammonium compound and a silicone emulsion. The gloves were then air dried, inverted and air dried again. Next, it was operated by wearing gloves. Overall, the glove showed good grip characteristics and wet wearing characteristics without the use of powder.

In summary, the articles of the present invention are characterized by improved wearability without the use of conventional lubricating powders. This article is easily worn by the presence of a wear layer formed from a styrene block copolymer. Styrene block copolymers can also be used to form the grip layer. Wearability can be further enhanced by forming a lubricating layer on at least a portion of the wear layer.
The present invention may be embodied in other specific forms without departing from the scope and spirit of its innovative characteristics. The embodiments of the present invention are therefore considered in all respects to be illustrative rather than restrictive, and the scope of the invention is indicated by the appended claims rather than by the foregoing description, and the appended claims All changes that fall within the meaning and range of equivalents of are therefore intended to be included within the scope of the present invention.

1 is a perspective view of an elastomeric article, i.e. a glove, according to the invention. FIG. 2 is an exemplary cross-sectional view taken along line 2-2 of the article of FIG. 1 including a substrate and a wear layer. FIG. 2 is an exemplary cross-sectional view taken along line 2-2 of the article of FIG. FIG. 2 is an exemplary cross-sectional view along line 2-2 of the article of FIG. 1 including a substrate, a wear layer, a grip layer, and a lubrication layer.

Explanation of symbols

26 Base 28 First surface 32 Wear layer

Claims (20)

A substrate comprising an elastomeric material and having a first surface;
A wear layer comprising a styrene block copolymer and overlying at least a portion of the first surface;
An elastomeric article comprising:   The article of claim 1, wherein the elastomeric material comprises a mid-block saturated styrene block copolymer.   The article of claim 1, wherein the elastomeric material comprises a styrene-ethylene-butylene-styrene block copolymer.   The elastomer material is natural rubber, nitrile butadiene rubber, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene block copolymer, styrene-butadiene block copolymer, synthetic isoprene, chloroprene rubber, polyvinyl chloride, silicone. The article of claim 1, selected from the group consisting of rubber, and combinations thereof.   The article of claim 1, wherein the styrene block copolymer comprises a styrene-butadiene-styrene block copolymer.   The article of claim 1, wherein the wear layer is present in an amount from about 0.1% to about 2.5% by weight of the article.   The article of claim 1, wherein the wear layer is present in an amount from about 0.25% to about 1.5% by weight of the article.   The article of claim 1, further comprising a lubricating layer overlying at least a portion of the wear layer.   The article of claim 8, wherein the lubricating layer comprises silicone.   The article of claim 1, wherein the article is a glove. A substrate comprising an elastomeric material and having a first surface and a second surface;
A wear layer comprising a styrene-butadiene-styrene block copolymer and overlying at least a portion of the first surface;
A grip layer overlying at least a portion of the second surface;
An elastomeric article comprising:   The article of claim 11, wherein the elastomeric material comprises a styrene-ethylene-butylene-styrene block copolymer.   The article of claim 11, wherein the grip layer comprises a styrene-butadiene-styrene block copolymer.   The article of claim 11, wherein the grip layer is present in an amount from about 0.1% to about 2.5% by weight of the article.   The article of claim 11, wherein the grip layer is present in an amount from about 0.25% to about 1.5% by weight of the article.   The article of claim 11, further comprising a lubricating layer overlying at least a portion of the wear layer. A method of preparing an elastomeric article comprising:
Preparing a substrate comprising an elastomeric material and having a first surface and a second surface;
Forming a wearing layer comprising a styrene-butadiene-styrene block copolymer on at least a portion of the first surface;
A method comprising the steps of:   The method of claim 17, further comprising forming a grip layer comprising a styrene-butadiene-styrene block copolymer on at least a portion of the second surface.   The method of claim 18, further comprising contacting the grip layer with a chlorine source.   The method of claim 17, further comprising forming a lubricating layer comprising silicone and a quaternary ammonium compound on at least a portion of the wear layer.

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