[0001 ^' ] The present application relates generally to methods of providing texture to polymeric surfaces, and to the resulting textured polymeric materials.

10002] Kassa et al.. _f US Pat. 8,119,200, describe a method of imparting texture on an ungelled surface of a non-foamed polymeric material that has been applied to a fabric glove. The method uses the forces applied to the ungelled surface by an aqueous foam solution. In the Kassam process, the surface must be treated, after contacting the foam solution, with an electrolyte solution, which electrolyte will have a gelling action .

[90031 Applicants have now discovered that such external foam processes can be greatly simplified by providing a sufficient polymer gelling reagent(s) in the foam treatment step. Applicants have discovered that the variety of textures can be expanded with a number of techniques. For example, the base polymeric material can be foamed. Also, th speed at which the externai foam collapses after contacting the polymeric layer affects the surface texture. Further, the time between contacting the external foamy solution and an aqueous washout affects the surface texture.

SUMMARY

100041 Provided in one embodiment is a method of forming texture on polymeric surface comprising: (I) providing a polymeric layer with a first side and a second side, wherein the polymeric layer Is made from a polymeric material that gels on contact with a gelling agent, and wherein first sid of the polymeric layer is gelled, with gelling extending into the polymeric layer but not to the second side; (If) contacting the second side of the polymeric layer with a foamy aqueous solution of surfactant (one or more), the aqueous foam being in the process of collapsing during the contacting, wherein the aqueous solution of surfactant is effective to gel the polymeric material; (III) applying a aqueous medium to the second surface with sufficient force or agitation so as to remove a portion of the polymeric material; and (IV) curing the remaining polymeric material without, following the contacting step, further contacting the polymer layer with a gelling component

[OO Sj Also provided is a method of forming texture on polymeric surface comprising: (A) providing a polymeric layer with a first side and a second side, wherein the polymeric layer is made from a polymeric material that ge!s on contact with a gelling agent, and wherein the first side of the polymeric layer is gelled, with gellin extending into the polymeric layer but not to the second side; (B) contacting the second side of the polymeric laye with a foamy aqueous solution of a caiionic surfactant (one or more), the aqueous foam being in the process of collapsing during the contacting, wherein the cationic surfactant is effective in the foamy aqueous solution to gel the polymeric material; (C) appiying a aqueous medium to the second surface so as to remove a portion of the polymeric material; and€ curing the remaining polymeric material.

DESCRIPTION OF THE DRAWINGS

[§006] So that the manner in which the above recited features of the present invention can be understood i detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only illustrative embodiments of this invention and are therefor not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.

Q007] FIG. 1A depicts a process of making the textured surface of the invention (for supported articles);

[0008] FIG. 1B depicts a process of making the textured surface of the invention (for unsupported articles);

[8009] F!Gs. 2A and 2B compare the process results where the externa! foamy aqueous solution lacks (2A) or further comprises (2B.) metal salt components; |Θ01Θ] FiGs. 3A to 3C compare the process results using amphoteric surfactant (3A), anionic surfactant (3B) and cationic surfactant (3C);

[©Oil] FiGs. 4A and 4B compare the process results where a shorter (4A) or longer (4B) delay between the two aqueous treatments is used; and

[0012] FiGs. 5A and 5B compare the process results where relatively iess

(5A) and relatively more (5B ungeiled polymer is present before contacting with the foamy aqueous solution.

{00131 To facilitate understanding, identical reference numerals have been used, where possible, to designate comparable eiements that are common to the figures. The figures are not drawn to scale and may be simplified for ciarity. It is contemplated thai elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.

DETAILED DESCRIPTION

1.0014] An "aqueous medium" is one is applied with force such as by spraying or dipping with agitation to wash off excess latex and surfactant. Such a solution/medium can for example contai one or more latex gelling agents, such as for example acids or salts. Without being bound by theory, these are believed to facilitate gelling and stabilizing texture formed with the contacting with aqueous foam. In embodiments, applicable to any embodiment described herein, the aqueous medium is not effective to gel the polymeric layer to which it is applied,

|0O15] "Cationic surfactant" in the foam aqueous solution is positively charged. Without being bound by theory, it is believed that these attract the negatively charged ions or anionic surfactants normally used as stabilizers in polymer suspension compositions (e.g., latex). A cationic surfactant can be for example a primar amine, secondary amine, tertiary amine, diamine, thamine, quaternary amine, quaternary amine, quaternary ammonia salts, ethoxylated amine, imidazole, a combination thereof, or the like. In a useful embodiment, cationic surfactant is used because it can gel the polymeric layer without the need for supplemental gelling agents. {Θ016Ι That the "cationic surfactant is effective in the foamy aqueous solution to gei the polymeric material with contact ^* means that the cationic surfactant can, and is present in amount effective to, gel the polymer material of the polymeric iayer. The use of the cationic surfactant in this amount is applicable to any embodiment described herein (having cationic surfactant, which can be in mixture with non-ionic, amphoteric, or anionic surfactant). Where other components of the foamy aqueous solution can reduce the effectiveness of the cationic surfactant, the amount of cationic surfactant is such that it. is effective given the inhibiting components.

{00.17) A "foamy aqueous solution" is one that will froth o appropriate agitation. In the claimed processes, the solution is froth during at least a portion of the time that It is contacted with the polymeric layer _* Despite the term "solution", non-dissolved components can be present so long as a texture- forming effect results from the foam action of the solution components,

[0018] "Gelling" encompasses coagulation. It is the transition of the polymer component from a form that easily washes out with water, to one that adheres to other polymer molecules and resists such wash out.

{0019) A "gelling component" as described herein is a material effective to gel a polymeric layer (namely the polymeric layer relevant to the context in which the term is used). If a component has a gelling agent, but not in an amount effective to provide such gelling property to the component, it is not a gelling component.

[0020] A "polymeric layer" as described herein can be formed of one, two, or additional dipping steps, as appropriate in the context. If for example, a first applied polymeric layer is allowed t substantially gel, so as for example to provide a fluid impervious layer, that layer will not be deemed part of a polymeric layer that is subject to the formation of texture with the external foaming process described herein. Polymeric compositions can be e!astomeric. Prior to gelling, polymeric compositions can be latex compositions. |Θ021Ι In embodiments, the polymeric compositions can be stabilized with cationic surfactant, and the foamy aqueous solution can utilize an anionic surfactant to gel in the absence or reduced presence of other gelling agents.

[0022| The polymeric layers (e.g., support or texture layers) may fee natural rubber latex (including Guayule latex), synthetic latex, or the like, and combinations thereof. The synthetic Iatex may be selected, for example, from the group comprised of polychloroprene, acrylonitrile butadiene copolymer (NBR) (such as carboxylaied acrylonitrile butadiene copolymer, such as highly carboxylated acrylonitrile butadiene copolymer), polyisoprene, polyurethane (PU), styrene-butadiene, butyl, and combinations thereof. For the texture-forming layer, NBR (i.e., nitri!e), polyurethane or a mixture thereof can be useful. For example, a latex can be used wherein the polymer component is about 95% to about 100% t. NBR, with the major part of the residual polymer component (if any) being PU. In such embodiments with PU, the PU component can be for example about 1 to about 5% wt. of the polymer components. A useful polyurethane is polyester based (e.g., WPU-70-18AW polyurethane, obtainable from Taiwan PU Corporation).

| 023| In embodiments, polymeric particle compositions may have commonly used stabilizers such as potassium hydroxide, ammonia, sodium salts, ethoxylated nonphenol, ethoxy!ated tridecyi alcohol, sulfonates and the like, in embodiments, the polymeric particle compositions ma contain other commonly used ingredients such as surfactants, anti-microbial agents, fillers/additives and the like, in embodiments, the polymeric particle compositions used to form the polymeric layer has a viscosity in the range of for example about 500-8000 centipoises, such as about 1000 - 5000 centipoises.

[Θ0 ] Embodiments according to the invention further include in the polymeric layer vulcanizing agents and activators, such as zinc oxide, zinc diethyl dithiocarbarnate (ZDEC), suiphur or thickeners, such as Rohagit SD-15 thickener (based on an aqueous dispersion of a thermoplastic methacrylic acid-acrylic ester copolymer, from Synthomer LLC, Atlanta, Ga), Acrysoi G111 thickener (neutralized polyacrylatem Dow), MHPC 50 thickener (nonionic cellulose ether, Ashland inc., Covington, KY), PVA 117 thickener ( uraray Co., Ltd., Osaka, JP) as are known to those of skill in the art. Particle fillers, i.e., reinforcement fillers, such as boron carbide and/or silicon carbide and/or, aluminum potassium silicates, such as mica, and/or aluminum oxide may be employed to improve the abrasion resistance of coatings formed from the polymeric compositions.

P025| Foamed or unfoamed polymeric layers can be used in the texture- providing layers, Foam polymer formulations can comprise elastomer, stabilizer, curative agent, and optionally foaming agent, one or more of thickening agent (e.g., MHPC), flow modifier, pigment(s), and the like. Wax or filler additives may be added. For a foamed polymeric layer, the air content in the composition can be for example in the 5 to 50% range o a volume basis. Once a composition is foamed with the desired air content and the viscosity is adjusted as appropriate, refinement of the foamed composition can be undertaken by stirring the composition with an impelle driven at a fast speed and using a different impeller run at a reduced speed to refine the bubble size as is known to those of skill in the art. Methods for incorporating high air contents are described in Woodford et al., US Pat 7,048,884, which is commonly-assigned and incorporated herein in its entirety.

[6026] Foamed or unfoamed polymeric compositions having higher viscosity may not penetrate the interstices between the yarns in the knitted liner and, if so applied _; may require a higher depth of immersion of a former having a dressed knitted liner. Also, the air cells can reduce the modulus of elasticity of the coating made from the polymeric composition, increasing the flexibility of the glove. The air content in the range of 5-15 volumetric percent results in foams that have closed ceils, creating a foamed coating that is liquid impervious and has a spongy, soft feel. Unfoamed polymeric compositions (0% air content) are used for example to create a texturized coating which is also impermeable to oil and water.

[Q027J Some air cells, whether an open-celled or close-celled foam may be disposed on the external surface of the coating, providing increased roughness and have the ability to remove boundary layer of oii and water from a gripping surface, providing increased grip properties, if the volumetric air content is in the range of 15-50% in a foamed coating on a liner, the air cells are adjacent to each othe and expand during a vulcanization heating step and touch each other, and merge. This process creates open-celled foams having an intra-foam network of ceils in fluid communication with each other. Therefore, open-celled foams absorb liquids, such as oils and water, into an internal matrix. For example, if a drop of liquid is placed on a glove in the palm portion, the liquid penetrates the polymeric coating cells, as opposed to a closed-celled foam, which is impervious to liquids.

10028) In embodiments, coagulant solution (e.g., 2-10 wt% calcium nitrate solution} is applied to the former or support article and dried prior to application of an e!astomeric layer.

When applying an polymeric layer, a gel!ied coagulant can be used to act as an adhesive for the latex to adhere to the former. The geliied coaguiant can contain for example calcium nitrate, wetting agent (alcohol ethoxyiate and/or a!kylaryiaikoxylafe), acids, celSulosic thickener, water-based defoamer and water. The formulation can be designed to have wetting agent(s) in order to have optimum former wetness to minimize potential of major defects such as holes and thin spots. The defoamer(s) function as bubble inhibitors (in the interior portion of layer that remains in embodiments relatively untextured (solid)).

[0030] Generally, for the polymeric layers on which texture is to be formed with the methods of the invention, a rougher texture is often formed when the layer is formed by a single dipping step. A relatively smoother texture is often formed with a layer formed by a double dipping process.

[0031] As discussed above, a variable that can be used to modify the type of texture obtained is the speed that the foam of the foamy aqueous solution collapses or so-called "internal rate of foamy aqueous solution collapses" causing physical reaction between latex coating & foamy aqueous solution upon contact , The speed of collapse can be measured by stopwatch. The collapsing time is in the range of 1 - 10 minutes, depending on the traveling time between contacting with foamy aqueous solution and applying aqueous medium. {Θ032Ι Generally, with a longer the delay time between contacting with foamy aqueous soiution and applying a aqueous medium (e.g. 6 - 10 minutes), the coating texture is deeper with smaller bubbles on the coating surface, if the delay is shorter (e.g. 1 - 2 minutes), generally the texture is shallower and relatively more bubbles on the surface.

18033] Generally, stirrers are used to create the foam in the foamy aqueous solution. For example, stirrers can be located at the end compartment or the bottom of a tank. The formers are dipped into the tank after the foaming process.

10034) Where the process uses a cationic surfactant to form the foamy aqueous soiution, the cationic surfactant can be necessary to the gelling action in the foamy aqueous soiution. That is to say that any other components that might have gelling action are not present in an amount sufficient to be effective in a commercially viable process absent the cationic surfactant. Also where the process uses a cationic surfactant to form the foamy aqueous soiution, the cationic surfactant can comprise substantially aii of the components with gelling action in the foamy aqueous solution. That is to say that the concentration all other components that have gelling action would have to be doubled in a commercially viable process to have gelling action absent the cationic surfactant. In the reaction process, the cationic surfactant ca effectively gel the polymeric materia! and enable fast texturization process to take place without the use of any gelling agent (other than surfactant).

Θ035] The amount of ungeiled polymer left on the article can affect texture formed. For example, the higher amount of ungeiled polymer depending on the latex gelling time and pick-up timing can result in relatively rough, dee texture, characterized b irregular surface shapes. The lower amount of ungeiled latex left on the knitted liner after the application of the foam aqueous soiution and aqueous medium can result in a finer, more shallow and more rounded surface topology. With spraying processes for applying aqueous medium, for example, the aqueous medium application can be measured by water flow rate and numbers of nozzles per spraying equipment. |0036] In embodiments that remove, a lesser amount of polymer, between about 10 % and about 30 % by weight of the polymer molecules applied to the texture-forming polymeric layer are removed by the aqueous medium, in embodiments that remove a greater amount of polymer, between about 30 % and about 50 % by weight of the polymer molecules applied to the texture- forming polymeric layer are removed by the aqueous medium.

[0037] In embodiments, the external foamy aqueous solution further comprises additional salt components (such as metal salt components). For example, it can be formulated in sea water. Fig. 2A shows the texture where a cationic surfactant (Algene 40) is used without salt. Fig. 2B shows the texture where a cationic surfactant (Algene 40) is used with salt (in the exemplification: the surfactant dissolved in sea water). With salt the indentations (indentations are darker in the figure) are more irregular and deeper. Without being bound by theory, it is believed that the irregular deep texture can be achieved with other surfactants. Fig. 2A shows Indentations of individual average diameter (taking into account oval or other shape irregularities) in the range of about 0.14 mm to about 0.80 mm, Fig. 2B shows Indentations of Individual average diameter in the range of about 0.14 mm to about 0.90 mm.

[0038] Where there is added salt, preferably the conductivity of the aqueous medium can be for example from about 0.01 S/cm to about 0.06 S/om.

[0039] Fig. 3A shows the texture where an amphoteric surfactant (Betaine) is used (see exemplary formulation below). Fig. 3B shows the texture where an anionic surfactant (Dowfax) is used (see exemplary formulation below). Fig. 3C shows the texture where a cationic surfactant (Algene 40) is used without salt (se exemplary formulation below). Compared with cationic, the texture in Fig. 3A is deeper and irregular. The texture in Fig. 3B is shallower than with cationic, more irregular than with cationic, and not as irregular as with amphoteric surfactant. Fig, 3A shows indentations of individual average diameter in the range of about 0.14 mm to about 0.60 mm; Fig. 3B in the range of about 0.10 mm to about 0.84 mm; Fig. 3C in the range of about 0.14 mm to about 1.0 mm. |Θ04Θ] Thus, parameters that can be varied to vary the texture of the surface include:

Selecting the type of surfactant- Selecting the aqueous solvent for the surfactant (such as including or not a metal salt component);

Selecting the delay time between contacting (i.e., withdrawing the polymer from the contacting solution) with the foamy aqueous soiution and applying a aqueous medium (such as by spraying). Generally, shorter delay times (such as 1 min.) result in relatively more indentations and shallower texture, and longer delay times (such as 6 to 10 min) result in relatively fewer indentations, and deeper texture. Compare FIG. 4A (1 min.) with FIG. 4B (-6-10 min.) (quaternary surfactant used to make both textures). (Fig. 4A shows indentations of individual average diameter in the range of about 0.10 mm to about 0.20 mm; Fig. 4B in the range of about 0.50 mm to about 0.80 mm.) Selecting for example (a) coagulant, (b) coagulant loading, (c) polymer latex stability or (d) the delay time between polymer application and contacting with the foamy aqueous solution, so as to modify the amount of ungelied latex present during the contacting with the foamy aqueous solution. Generally, higher amounts of ungelied polymer results in rougher, deeper texture, while Sower amounts result in finer, shallower texture. Generally, higher amounts of ungelied polymer results in indentations with more irregular shape, whil lower amounts result in rounder indentations. Compare FIG. 5A (relatively less ungelied polymer) with FIG. 5B (relatively more ungelied polymer) (quaternary surfactant used to make both textures). (Fig. 5A shows indentations of individual average diameter in the range of about 0.30 mm to about 0.60 mm; Fig. 4B in the range of about 0.30 mm to about 2.0 mm.)

{§8411 The contacting step is ended by removing the polymeric laye from the foamy aqueous soiution (including the foara that may be on top). This is so even though the removed polymeric layer may carry some of the solution with it. {Θ042Ι In certain embodiments, the amount of time between contacting step and the applying step is between about 0.1 and about 3 minutes, in certain embodiments, the amount of time between contacting step and the applying step is between about 4 and about 20 minutes.

[Θ0 3] In certain single dip embodiments, the amount of polymer removed by the contacting and aqueous medium application steps is from about δ % wt to about 35 %. in single certain dip embodiments, the amount of polymer removed is from about 35 % wt to about 55 %. The amount can be measured by comparing dry weight of the product with the two steps applied, to that with the step omitted. If the article is supported, the support weight is deducted from both measurements.

[0044] In multiple dip embodiments, those of skill will recognize which layers are adapted to be stable to the contacting and aqueous medium application steps. The weight of these stable layers and any support is deducted from the removal percentage calculation. In certain such embodiments, the removal percentage of the susceptible layers is as described in one of the above ranges.

[Θ045] In embodiments, the process is used to make interior or exterior surfaces for wearable articles, such as gloves, booties, elbow or knee guards, condoms, and the like. The textured pofymeric layer can be applied directly of via intermediate polymer to a fabric, such as a knitted, woven or non-woven fabric. In embodiments the articles are formed of polymeric layers (i.e., without fabric). [§046] A common use of the process is to provide gri texture on the exterior of an article. Another use is to enhance oil or wafer absorption of open foam polymeric materials. This use can be on the exterior, to help preserve grip in the presence of water or oil, or on the interior to aid in moisture management. Grip on the interior may be important in some contexts, such as to limit slippage of elbow or knee guards.

[Q047J As exemplified in FIG. 1A, a dipping former (typically cleaned) has a fabric loaded thereon (Step 202). In embodiments, the former already has fabric with laminated polymer adhered, and at least one further laminated layer of

- 1 i - polymer is applied per an iteration of step 210. A laminate is a bonding, fusing, adhesion, or the like between polymer layers, o between polymer and fabric layers, such that in the range of anticipated use the laminate is a unitary structure.

[Θ0 8] in Step 204, the former is heated (the asterisk here and elsewhere in the figure denoting an optional step). In Step 206, a coagulant composition is applied. In Step 208, the coagulant composition is dried, in Step 210, polymer is applied. In Steps 212 and 214, the former is removed from the polymer composition for dripping {can be upward and/or downward) and air drying (can be upward and/or downward). In Step 216, polymer application is repeated (Step 210) one or more times, also repeating in order as appropriate to the process Steps 210, 212 and 214 (optionally repeating coagulant coating as well). In Step 218, the polyme coating is contacted with external foamy aqueous solution. For this step, the solution can be agitated or otherwise aerated to reduce density to an appropriate amount, such as about 90%. In Step 220, the aqueous medium is applied. In Step 222, the article is leached. In Step 224, the exterior polymer layer Is chlorinated. (In practice, those steps marked with an asterisk are conducted or not as a design choice.) In Step 226, the polymeric layer is cured. Typically, an article comprising the polymeric layer is stripped from the former for packaging or use.

[0049] The process for an unsupported glove is set forth in Fig. 1B. The numbering corresponds to the numbering above, except that the step 204 is now step 304 (+100), etc. (There is no analog of step 202.) In embodiments, the former already has polymer adhered, and at least one further layer of polymer is applied per an iteration of step 310.

(0050] While many of the steps in Figures 1A and IB are nearl always done (unless marked with an asterisk), the invention involves: a polymer layer to which coagulation is occurring from the underside; contacting the topside with the foamy aqueous solution; and contacting the topside with the aqueous medium, [0051 J The surfactant components in the externa! foam can be for example anionic, amphoteric, non-ionic or cationic surfactants, or mixtures thereof. Anionic surfactant can be for example Dowfax 2A1 (Alkyldiphenyioxide Qisulfonate, Dow Chemical, Newark, DE), Empimin OT 75 (dioctyl sodium sulfosuccinate, Hunstman Holland), or a mixture thereof. For example, the anionic surfactant treated glove has shallow texturization with irregula bubbles shape. Amphoteric surfactant can be, for example, sulfamic acid, amino propionic acids, or a mixture thereof. For example, the amphoteric surfactant treated glove has deep texturization with irregular bubbles shape. Non-ionic surfactant can be, for example, Surfyno! 465 (Ethoxylaied aceiy!enic diois, Air Products), ZetaSperse 179 (Ethoxylaied alcohols, Air Products), Teric 188 (Fatty alcohol - alky!ene oxide copolymer, Hunstman), or a mixture thereof. Cationic surfactant can be for example, Tn ^' ameen Y12D-30 (Dodecyl dipropyienetriamine, Akzo Nobel), Triameen T (N-tallowalkyl dipropySene triamine, Akzo Nobel), Puomeen (OleySpropy!enediamine, Akzo Nobel), Redicote 103 (mixture of N- Ta!low-1 ,3-diaminopropane and (Hydrogenated tallow) amine, Akzo Nobel), Berol 1250 (Tal!ow alkyla ine, Akzo Nobel), Fentacare T05 (Ethoxylaied tallow alkyl amine, Solvay), Servamine Koo 380 (Oleic acid & diethySenein ^' amine, E!ementis) or a mixture thereof.

|Θ052| Specific embodiments according to the methods of the present invention will now be described in the following examples. The examples are illustrative only, and are not intended to limit the remainder of the disclosure in any way .

10053 J Articles with textured surfaces that can be made with the methods of the invention include for example, gloves, foot coverings (e.g., booties, such as surgical booties), f inger cots, condoms, coverings for objects that are gripped, carpet grips, and the like.

(Θ054] In embodiments, the oil grip force fo gloves made according to the invention (with finger tips textured per the invention) is about 5.01 kgf or less with at 6.5 kg challenge. In embodiments, the oil grip force for gloves made according to the invention is about 2.82 kgf or less with at 4.5 kg challenge. In embodiments, the oil grip force for gloves made according to the invention is about 1.27 kgf or less with at 2.5 kg challenge. In embodiments, the surface on another articie thai is not such a glove is made by a method that would provide such oil grip, and has substantially corresponding surface topology.

[ΘΘ55] in certain embodiments, the indentations are of individual average diameter of about 0.15 mm to about 2.2 mm, with a disperse range of diameters, and with an irregular, bulbous shape to the majority of the indentation boundaries (se Fig. 58). This sizing means that for a representative area including 200 indentations, 80% are in the size range, A disperse range means that in the representative area 25% or more of indentations are 40% of the mean diamete or less, and 25% or more of indentations are 60% of the mean diameter or more.

Principle of the Test Method

[0056] A test bar with interna! sensors that detect grip force (units in kgf) is connected at one end by a cable that passes over and is suspended from an overhead pulley and then connects down to a bucket container on the floor. The bucket is filled with water to provide a certain load of 23 kg, 4.5 kg or 6.5 kg. A tester wearing a glove specimen grasps a test bar to provide a minimal force to secure contact and grip so that a certain load (2.5 kg, 4.5 kg & 6.5 kg} can be lifted. The grip force applied on the test bar is then displayed on the digital indicator. The test bar and gloves are covered with water or oil when performing wet and oil grip test, respectively. The wet grip test differs from the oil grip test only in substituting water for the oil. The oil used is Shell Rimuia X 15W-40 (Shell Oil Co.), with a dynamic viscosity at -20°C of 6600 mPa.

Test Procedure for Oil Grip fTabie) a) A bucket is placed on a 30 kg balance and filled with tap water to provide a weight of 2.5 kg.

b) 5 ml of Shell Rimuia X 15W-40 is used to apply on the glove specimen.

c) The test bar is then covered with Shell Rimuia X 15W-40 by rubbing it with the test glove specimen which has early wetted. d) The tester uses ideally the same hand to grasp the test bar wearing the test glove specimen.

e) The gloved hand applies just sufficient grip force to the test bar to provide secure contact and grip so that with a downward movement of the tester's arm the weight could be lifted.

f) The grip force (i kgf) applied on the test bar is then displayed on the Digital Indicator in two decimal places.

The tester shall try several attempts to Sit up a certain load and observe any penetration of Shell Rimula X 15W-4Q into the tester's hand.

h) The bucket is placed on a 30 kg balance and filled with tap water to provide a weight of 4.5 kg.

i) Repeat steps 5.7.2 (C) b) - g) for lifting up the load of 4.5 kg.

j) The bucket is placed on a 30 kg balance and filled with tap water to provide a weight of S.5 kg.

k) Repeat steps 5.7.2 (C) b) - g) for lifting up the load of 6.5 kg.

[§057] Ail ranges recited herein include ranges therebetween, and can be inclusive o exclusive of the endpoints. Optional included ranges are from integer values therebetween (or inclusive of one original endpoint), at the order of magnitude recited or the next smaller order of magnitude. For example, if the lower range value is 0.2, optional included endpoints can be 0.3, 0.4, ... 1.1 , 1.2, and the like, as well as 1 , 2, 3 and the like; if the highe range is 8, optional included endpoints can be 7, 8, and the like, as well as 7.9, 7.8, and the like. One-sided boundaries, such as 3 or more, similarly include consistent boundaries (or ranges) starting at integer values at the recited order of magnitude or one lower. For example, 3 or more includes 4 or more, or 3.1 or more.

[0058] Where a sentence states that its subject is found in embodiments, or in certain embodiments, or in the like, it is applicable to any embodiment in which the subject matter can be logically applied. EXAMPLE 1

[0059] Exemplary components, and exemplary amounts for the foamy aqueous solution of surfactant include:

8M®\ The foamy aqueous solution of surfactant can be agitated to reduce densiiy to, for example, about 90%, and used immediately thereafter to contact the polymeric layer.

0061] For amphoteric surfactant, an exemplary formulation is: 0 Water 0,0 94.09 14.11

42.5 Phosphoric acid 0.30 0.71 0.106

100 Acetic acid 0.24 0.24 0.04

30 Beta ί tie 0.08 0.27 0.04

100 Sodium Chloride 4.70 4.70 0.71

Total 5.32 100.00 15.00

[0062] For anionic surfactant, an exemplary formuiation is:

[f?063| For cationic surfactant, an exemplary formulation is;

|Q064| For cationic surfactant, an exemplary formulation is: 0 Water 0 96.67

30 Triameen Y12D-30 1 3.33

Total 1 100

Numbered Embodiments

[0065] The invention can be further described wit reference to the following Embodiments:

[0066] Embodiment 1. A method of forming texture on polymeric surface comprising: (I) providing a poiymeric layer with a first side and a second side, wherein the poiymeric layer is made from a polymeric material that gels on contact with a gelling agent, and wherein the first side of the polymeric layer is gelled, with gelling extending into the polymeric layer but not to the second side; (IS) contacting the second side of the polymeric layer with a foamy aqueous solution of surfactant (one or more), the aqueous foam being in the process of collapsing during the contacting, wherein the aqueous solution of surfactant is effective to ge! the poiymeric material; (111) applying a aqueous medium to the second surface with sufficient force or agitation so as to remove a portion of the polymeric material; and (Ml) curing the remaining poiymeric materia! without, following the contacting step, further contacting the polymer layer with a gelling component.

100671 Embodiment 2. A method of forming texture on polymeric surface comprising: (A) providing a polymeric layer with a first side and a second side, wherein the polymeric layer is made from a polymeric materiai that gels on contact with a gelling agent, and wherein the first side of the polymeric layer is gelled, with gelling extending into the polymeric layer but not to the second side; (6) contacting the second side of the polymeric layer with a foamy aqueous solution of a cationic surfactant (one or more), the aqueous foam being in the process of collapsing during the contacting, wherein the cationic surfactant is effective in the foamy aqueous solution to gel the poiymeric material; (C) applying a aqueous medium to the second surface so as to remove a portion of the polymeric material; and (D) curing the remaining polymeric material

[ΘΘ68] Embodiment 3. The method of one of the foregoing Embodiments, wherein the foamy aqueous solutio would be, in the absence of the surfactant, ineffective to so gel

P069| Embodiment 4. The method of one of the foregoing Embodiments, wherein the aqueous medium is applied by spraying.

[0070] Embodiment 5. The method of one of the foregoing Embodiments, wherein the foamy aqueous solution comprises an amphoteric surfactant.

{0071 J Embodiment 6. The method of one of the foregoing Embodiments, wherein the foamy aqueous solution comprises an anionic surfactant.

f0072j Embodiment 7. The method of one of the foregoing Embodiments, wherei the foamy aqueous solution has conductivity from about 0.01 S/cm to about 0.08 S/cm (wherein at least at the higher end of this range Embodiment 3 is less likely to apply).

[0073] Embodiment 8. The method of one of the foregoing Embodiments, wherein an amount polymer of susceptibte layers removed by the contacting and aqueous medium application steps is from about 5 % wt to about 35 %.

{0074] Embodiment 9. The method of one of the foregoing Embodiments, wherein an amount polymer of susceptible layers removed by the contacting and aqueous medium application steps is from about 35 % wt to about 55 %,

[0075] Embodiment 10. The method of one of the foregoing Embodiments, wherein an amount of time between contacting step and the applying step is between about 0.1 and about 3 minutes.

{0076] Embodiment 11.... The method of one of the foregoing Embodiments, wherein an amount of time between contacting step and the applying step is between about 4 and about 20 minutes.

P077] Embodiment 12. A method of forming texture of one of the foregoin Embodiments, wherein the curing is conducted without, following the contacting step, furthe contacting the second side of the polymer layer with a gelling component. |Θ078] Embodiment 13. The method of one of the foregoing Embodiments, wherein the first side of the polymeric layer is directiy, or via one or more polymeric layers, laminated ^' to a fabric liner.

I0079J This invention described herein is of a textured glove and methods of forming the same. Although some embodiments have been discussed above, other implementations and applications are also within the scope of the following claims. Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merel illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and thai other arrangements may be devised without departing from the spirit and scope of the present Invention as defined by the following claims.

|i080j Publications and references, including but not limited to patents and patent applications, cited in this specification are herein incorporated by reference in their entirety in the entire portion cited as if each individual publication or reference were specifically and individually indicated to be incorporated by reference herein as being fully set forth. Any patent application to which this application claims priority is also incorporated by reference herein in the manner described above for publications and references.