Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/02—Direct processing of dispersions, e.g. latex, to articles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C33/00—Moulds or cores; Details thereof or accessories therefor
  • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
  • B29C33/60—Releasing, lubricating or separating agents
  • B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
  • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
  • B29C41/14—Dipping a core
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
  • B29C41/34—Component parts, details or accessories; Auxiliary operations
  • B29C41/38—Moulds, cores or other substrates
• • A—HUMAN NECESSITIES
  • A41—WEARING APPAREL
  • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
  • A41D19/00—Gloves
  • A41D19/0055—Plastic or rubber gloves
  • A41D19/0058—Three-dimensional gloves
  • A41D19/0062—Three-dimensional gloves made of one layer of material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2307/00—Characterised by the use of natural rubber

Definitions

• the present invention relates to the use of a polymeric release composition for molds and formers used in the production of natural and synthetic rubber articles.
• the polymeric release composition is useful for the formation of latex gloves, and also for preventing blocking on the outer surface of such gloves.
• the release composition of the present invention has the advantage of being easily cleaned from molds and formers, and is compatible with coagulant currently used in many manufacturing processes, eliminating the need for an extra step to coat the mold or former with a release coating.
• latex glove or latex article refer to a glove or article made of natural or synthetic rubber.
• Articles made from natural or synthetic rubber are elastic materials having low glass transition temperatures. The surfaces of these materials are tacky and tend to adhere to each other.
• latex gloves are difficult to strip from glove formers at the end of the manufacturing process, and they tend to stick together, or block, when packaged for distribution and sale.
• One method involves the use of a particulate or powder material, such as starch, talc, or calcium carbonate.
• the particulate can be blended into a coagulant solution to form a barrier between the latex rubber and the surface of the former.
• the powder facilitates the stripping of gloves from the formers, and also prevents blocking.
• the powder coating is a known nuisance, as loose powder can become airborne.
• Starch powder tends to adsorb proteins found in natural rubber latex and the powder is easily dislodged during use, contaminating the surrounding environment and causing allergies and other negative effects.
• the protein/powder complex serves as a food source for bacteria, allowing them to proliferate.
• Polymeric mold release agents have also been disclosed in the art.
• Formulated polychloroprenes are described in EP 0 640623, Urethane dispersions in U.S. Patent Number 5,534,350, and Styrene/acrylates containing silicone in U.S. Patents Numbers 5,993,923; 5,691 ,069; 5,700,585; and 5,712,346.
• Copending U.S. Patent Application 09/400,488, and copending U.S. Patent Application, submitted September 15, 2000 describe the use of star polymers as inner coatings for latex gloves.
• a release composition containing a water-borne high Tg polymer formed from at least one hydrophobic monomer and at least one hydrophilic monomer provides a powder-free mold release agent, provides anti-blocking in the finished article, and also aids in providing a smooth latex deposition on the formers. Additionally, the release composition is dispersible in high electrolyte coagulant, making it compatible with current manufacturing processes.
• the present invention is directed to a mold or former for natural or synthetic rubber articles having on its surface a release composition comprising a water-borne polymer formed from at least one hydrophobic monomer and at least one hydrophilic monomer, where the polymer has a Tg of at least -10°C.
• a release composition containing a water-borne polymer, having a Tg of at least -10°C, and formed from at least one hydrophobic monomer and at least one hydrophilic monomer, is applied to a former as a release coating.
• Still another embodiment of the invention is a natural or synthetic rubber article having on its surface a coating comprising a polymer having a Tg of at least -10°C, and formed from a hydrophobic monomer and a hydrophilic monomer.
• Still another embodiment of the invention is a latex coagulant, comprising a release composition, comprising a polymer having a Tg of at least -10°C, and formed from a hydrophobic monomer and a hydrophilic monomer, which is used in manufacturing powder-free rubber articles.
• the key performance characteristics desirable for a release coating are: a high Tg polymer, which provides anti-blocking; ease of cleaning from a former; wettability of the film, for smooth latex deposition; an affinity to the latex surface; the ability to impart an anti-blocking character to the article formed from a mold or former.
• the present invention is directed to a mold or former for the production of natural and synthetic rubber articles, having on its surface a release composition comprising a water-borne high Tg polymer formed from at least one hydrophobic monomer and at least one hydrophilic monomer.
• Natural and synthetic rubber articles refer to articles made from low-Tg, tacky polymeric materials.
• examples of such materials include, but are not limited to, butyl rubber, natural latex rubber, polyvinyl chloride, neoprene, nitrile, viton, styrene butadiene copolymers, polyurethanes, or interpenetrating polymer network emulsion polymers, or combinations of these.
• the water-borne polymer of the present invention is one which is water-borne, and formed by means known in the art, such as emulsion polymerization and suspension polymerization.
• high Tg polymer is meant a polymer having a Tg of at least -10°C, preferably from 25 to 200°C, and most preferably from 40 to 150°C.
• Monomers useful in forming the polymer of the present invention are ethylenically unsaturated monomers or mixtures thereof.
• Particularly useful hydrophobic monomers include (meth)acrylates, vinyl acetate, ethylene, and styrene.
• a preferred hydrophobic monomer is styrene.
• the polymer of the present invention is also formed from a hydrophilic monomer.
• the hydrophilic monomer is present in the polymer at from 10-90 percent, based on the weight of the polymer.
• Suitable hydrophilic monomers include those monomers that are ionic, e.g. anionic, cationic, or zwitterionic, or have sufficient nonionic polar functionality, e.g. hydroxyl or amido groups to render them hydrophilic.
• Examples of such monomer include, but are not limited to hydroxyethyl acrylate, acrylonitrile, 2-(dimethylamino)ethyl (meth)acrylate, [3-(methacryloylamino)propyl]trimethylammonium chloride, 2- acrylamido-2-methyl-1-propanesulfonic acid sodium salt (a.k.a. AMPS), [2- (acryloyloxy)ethyl]trimethylammonium chloride.
• Preferred hydrophilic monomers are acrylic acid and methacrylic acid.
• the polymer may optionally contain a cross-linker.
• the cross-linker is present at from 0 to 10 percent, and preferably from 0.5 to 5 percent by weight, based on the weight of the polymer.
• the cross-linker is preferably a di-functional cross-linker, such as divinylbenzene, diallyl maleate, ethylene glycol dimethacrylate, vinyl crotonate and diallyl phthalate.
• Multi-functional cross-linkers such as allyl and vinyl sucrose ethers, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, and the like, can also be used.
• the emulsion polymer of the present invention has an average particle size as measured by photon correlation spectroscopy in the range of from 0.05 to 1.5 microns, preferably from 0.15 to 0.9 microns, and most preferably from 0.2 to 0.6 microns.
• the particle size may be adjusted by means known in the art such as polymer seeding, initiator concentration, control of the salinity, water-hardness, surfactant concentration, type of surfactant, and by temperature effects on the surfactant solubility and initiator decomposition rate. It has been found that the particle size of the emulsion polymer is critical for proper anti-blocking properties. The particle size is also important to coagulant resistance. Particles that are too small have a poor resistance to a coagulant, while particles that are too large can settle in a dilute coagulant solution.
• the release composition may optionally contain other ingredients, such as dispersants, surfactants, microspheres, and rheology modifiers.
• Surfactants useful in the present invention include, but are not limited to: anionic, cationic, nonionic, and amphoteric surfactants; and polymeric surfactants including but not limited to linear and star copolymers.
• the surfactant improves the uniformity of the latex deposition, improves the ease of stripping and improves the wettability of the coated former by the latex.
• the release coating contains no silicones, however the addition of a silicone to the composition can also be advantageous.
• a problem with having silicon compounds in the release composition is that they can remain on a mold or former, making the mold or former more difficult to clean.
• the release composition may also contain microspheres.
• Microspheres are useful in reducing the surface contact area, and thus the adhesion between the coated rubber article and the mold, former, or other object. This improves both the release and anti-blocking characteristics.
• the microspheres have diameters below 60 microns, preferably from 5 to 40 microns, and most preferably from 10 to 30 microns.
• the microsphere may be made of any material that is harder than the article being coated.
• microspheres useful in the present invention are those made of polyamides such as nylons, polymethylmethacrylate, polystyrene, polyethylene, polypropylene, polytetrafluoroethylene, polyesters, polyethers, polysulfones, polycarbonates, polyether ether ketones, and other polymers and copolymers, silica, and microcrystalline cellulose.
• the microspheres are present in the release composition at from 0.05 to 5 percent by weight, and most preferably at from 0.1 to 1 percent by weight.
• a dispersant may optionally be added to aid in dispersion of the microspheres into the aqueous release composition.
• Dispersants useful in the present invention include, but are not limited to, surfactants and polymeric dispersants including amphiphilic linear and star copolymers.
• a rheology modifier is optionally present in the release composition. The rheology modifier is used to control the viscosity of the composition for ease of use in different manufacturing processes and equipment, and to control the uniformity and thickness of the coating.
• Rheology modifiers useful in the present invention include, but are not limited to cellulosics such as hydroxyethylcellulose, cationic hydroxyethylcellulose, such as polyquaternium-4 and polyquatemium-10, hydrophobically modified hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, and hydroxypropylcellulose; dispersed or soluble starches or modified starches; and polysaccharide gums such as xanthan gum, guar gum, cationic guar gum such as guar hydroxypropyltrimonium chloride, and locust bean gum.
• Other suitable rheology modifiers include but are not limited to acid soluble copolymers, surfactants, etc. The rheology modifier is typically added at from 0.01 to 10 percent by weight, and preferably from 0.02 to 3 percent by weight, based on the release composition.
• the release composition may also contain other additives known in the art, such as adhesion promoters, crosslinking agents, biocides, low surface energy compounds, fillers, and anti-foaming agents.
• the release composition of the present invention is made by combining each of the ingredients to form an aqueous dispersion, by means known in the art.
• the polymeric release coating may be used to coat a variety of materials used as molds and formers of natural and synthetic rubber articles.
• the molds and formers may be of any material known in the art, including but not limited to ceramics, glass, and stainless steel. Items produced in the molds or formers include gloves, prophylactics, catheters, tires, swimming caps, balloons, tubing, and sheeting.
• a particularly suitable end use application is as a release composition in the production of latex gloves, including surgeons' gloves, physicians' examining gloves, and workers' gloves, more particularly powder-free latex gloves.
• the polymeric coating composition When used to coat the molds or formers in the preparation of gloves, the polymeric coating composition may be applied using several different methods. For example, in one method for coating the glove mold or former, a former or mold in the shape of a hand is dipped into a solution or dispersion containing the release composition, then dipped into a coagulant mixture containing a latex coagulant.
• Useful coagulants include, but are not limited to, calcium nitrate and calcium chloride.
• a clean former or mold in the shape of a hand is dipped into a coagulant containing a release composition. After drying, the mold coated with the release coating and coagulant can be used to prepare a glove by methods known in the art.
• the coated mold is immersed in a natural or synthetic rubber latex for a time sufficient for the rubber to coagulate and form a rubber coating of the desired thickness.
• the glove then may be water leached to remove impurities from the rubber.
• the formed glove is then oven cured, cooled, and dipped into a coating composition, which will become the inner glove coating.
• the formed glove can be dipped into a coating composition prior to the oven cure and cooling.
• the inner surface treatments include, but are not limited to those known in the art, including polymers such as that described in U.S. Patent Application Number 09/663,468 incorporated herein by reference, other polymer coatings, chlorination, and starch or clay powders.
• the glove is simultaneously stripped from the mold and inverted. Some, or all of the release coating on the glove mold or former is transferred to the what has become the outer surface of the glove.
• the release composition and the coagulant can be combined into the same solution or dispersion.
• the release composition of the present invention is compatible with coagulants currently used in the production of rubber articles.
• the combination of the coagulant and release composition into the same processing step allows manufacturers to use the release composition in current processes without the need for costly modifications or the need for additional processing steps.
• the polymer composition of the present invention is useful as a release agent in other industries, including but not limited to: injection molding, C-V joints, and in the manufacture of tires, synthetic gloves, and other rubber articles.
• Articles formed using the release composition of the present invention possess good anti-blocking properties. This property prevents adhesion between articles, such as latex gloves, which are packed together, but must be easily separated from each other for use.
• a latex glove can be made by:
• Method B Making a latex glove with a formulated coagulant
• a latex glove can be made by:
• a resin kettle equipped with a mechanical stirrer, nitrogen inlet, thermometer, and two slow addition feeds was charged with water (391 g), TOMADOL 1-3 (13.8 g), and LUBRHOPHOS LB-400 (8.6 g). This stirred mixture was warmed to 65 °C while flushing with nitrogen. To this mixture was added 5% of a well mixed pre-emulsion prepared from the slow addition of premixed styrene (83.5 g), methacrylic acid (MAA) (177.5 g), and ethylene glycol dimethacrylate (2.4 g) to a stirred premixed solution of LUBRHOPHOS LB-400 (8.6 g), TOMADOL 1-3 (13.8 g), and water (216 g). After this addition was complete, the reaction vessel was charged with an initial catalyst of sodium persulfate (0.2 g in 16.8 g water) and the reaction mixture was allowed to warm to 80 °C
• the reaction mixture was simultaneously charged with the pre- emulsion over 180 minutes and a sodium persulfate solution (0.27 g in 60 g water) over 210 minutes.
• a sodium persulfate solution (0.27 g in 60 g water) over 210 minutes.
• the remaining monomer was scavenged by the addition of terf-butyl hydroperoxide (1.2 g in 2 g water), followed by the addition of ferrous ammonium sulfate (0.3 g of a 2% solution dissolved in 5 g water) 30 minutes later, then the slow addition of erythorbic acid (1.2 g in 10 g water) over the next 30 minutes.
• the reaction mixture was then cooled, filtered through an 80 mesh filter, and used for the formulation without additional purification.
• the emulsion product contains 30% solids with 68 parts MAA, 32 parts styrene and 1 part cross-linker.
• the Tg of the polymer was estimated to be 115 S C using MSI
• polymer solution from example 1 500g was added to a 2-gallon container. 4500g of coagulant solution (containing 10% calcium nitrate or 5% calcium chloride) were then slowly introduced while stirring. The polymer was stable in the coagulant dispersion, but mild flocculation was observed. Slight sedimentation was found over time but this can be easily redispersed. The polymer containing coagulant can last several weeks without changing the properties.
• coagulant solution containing 10% calcium nitrate or 5% calcium chloride
• the leached latex deposit was then dried and dipped into a polymeric inner surface treatment solution to coat the inner surface.
• the polymer treated glove was then vulcanized at 90-
• the latex glove was easily stripped from the mold.
• the 2-side polymer treated latex glove was powder free, with the inside surface exhibiting good donnability and the outside surface exhibiting anti-blocking and non-slippery grip.
• the mold was then immersed into a 1 molar KOH alkaline solution and rinsed with water to remove residual polymer.
• the cleaned mold was used for new latex depositions.
• Example 4 Making a powder free glove using method A
• example 1 in water.
• the mold was then dried at 70°C for 1-4 minutes and immersed for 10-20 seconds into a regular coagulant (10% calcium nitrate aqueous solution or 5% calcium chloride).
• the coated mold was then partially dried and immersed into natural rubber latex at room temperature for 20-30
• the leached latex deposit was then dried and dipped into a polymeric inner surface treatment solution to coat the inner surface.
• the latex glove was easily stripped from the mold.
• the 2-sided polymer treated latex glove is powder free, with the inside surface exhibiting good donnability and the outside surface exhibiting anti-blocking and non- slippery grip.
• the mold was cleaned by immersing into a 1 molar KOH alkaline solution and rinsing with water to remove remaining polymer. The clean mold was used for new latex depositions, with no degradation in glove quality.
• Example 5 Making powder free latex gloves with emulsion polymers with different Tg's
• Emulsion polymers were made as in example 1 with different Tg's by varying the monomer compositions. All polymers contained 1 part per hundred monomer (pphm) of a difunctional cross-linker.
• Emulsion polymers were made as in example 1 with different cross-linker (ethylene glycol dimethacrylate) amounts.
• the cross-linker parts per hundred monomer (pphm) varied from 0 pphm, 0.5 pphm, 1 pphm, 2 pphm, 3 pphm, 4 pphm to 5 pphm. Gelling was noted at 5 pphm cross-linker.
• These polymers with the exception of the one containing 5 pphm cross-linker, were used as release agents in the preparation of powder free latex gloves, using Method B at 3% polymer concentration. All polymers produced uniform latex deposition and the stripped molds were easy to clean.
• Zero pphm cross- linker showed reduced mold release and anti-blocking. All other polymers showed very good anti-blocking and mold release.
• Four pphm cross-linker showed exceptional ease of stripping.
• Example 7 Making powder free latex gloves with emulsion polymers of different acid level
• Emulsion polymers were made as in example 1 with different acid levels. All polymers contained 1 pphm ethylene glycol dimethacrylate cross-linker.
• the 80% MAA reaction gelled The 80% MAA reaction gelled. These polymers, with the exception of the one containing 80% MAA, were used as release agents in the preparation of powder free latex gloves, using Method B at 3% polymer concentration. Zero and 5% MAA showed good anti-blocking and mold release. All others showed very good anti-blocking and mold release. Polymer 7D exhibited long time stability in the coagulant mixture.
• Example 8 Making powder free latex gloves with emulsion polymers containing methyl methacrylate (MMA) Polymer emulsions were prepared according to example 1 using methyl methacrylate (MMA) in place of styrene. All polymers contained 1 pphm ethylene glycol dimethacrylate cross-linker.
• MMA methyl methacrylate
• Example 9 Making powder free latex gloves with emulsion polymers containing other hydrophobic monomers
• Polymer emulsions were prepared according to example 1 using other hydrophobic monomers in place of styrene (table 4).
• Monomers for polymers 9A-C include cyclohexyl methacrylate (CHM), isobomyl methacrylate (IBXM), and dicyclopentanyl acrylate (DPA). All polymers contained 1 pphm of a difunctional cross-linker. These polymers were used as release agents in the preparation of powder free latex gloves, using Method B at 3% polymer concentration. All samples gave acceptable anti-blocking and mold release.
• CHM cyclohexyl methacrylate
• IBXM isobomyl methacrylate
• DPA dicyclopentanyl acrylate
• Example 10 Making powder free latex gloves with surfactants
• a series of non-ionic surfactants including BRIJ and TWEEN from ICI, and SURFYNOL from Air Products, were used as release agents in the preparation of powder free latex gloves, using Method B.
• the concentration of the surfactants was 2% in the release coatings.
• the latex deposit was uniform and the stripped formers were very easy to clean.
• the latex glove was easily stripped off the mold, but exhibited poor anti-blocking.
• Poly(methyl methacrylate) (PMMA) beads with particle size around 20 ⁇ m were dispersed in a regular coagulant solution (containing 10% calcium nitrate or 5% calcium chloride). The weight percentage of beads was 3% in the total solution.
• This dispersion was used as a release agent in the preparation of powder free latex gloves, using Method B.
• the latex glove was hard to strip off the former.
• Example 12 Making powder free latex gloves with a thickener Xanthan gum was dissolved in a regular coagulant solution, containing 10% calcium nitrate or 5% calcium chloride. The concentration of xanthan gum in the formulated coagulant was 0.04%.
• This dispersion was used as a release agent in the preparation of powder free latex gloves, using Method B. The latex gloves were hard to strip off the formers and showed poor anti-blocking.
• Example 13 Making powder free latex gloves with a polymer and a thickener
• a formulated coagulant containing 0.04% xanthan gum and 3% polymer from example 1 was prepared. This dispersion was used as a release agent in the preparation of powder free latex gloves, using Method B. The outside polymer coating was more uniform than in example 3.
• Example 14 Making powder free latex gloves with beads, a surfactant, and a thickener
• a formulated coagulant containing 0.3% Beads, 0.1% SURFYNOL-465 and 4% CaCI 2 was prepared. This dispersion was used as a release agent in the preparation of powder free latex gloves, using Method B. The outside coating was uniform, but the latex gloves were hard to strip off the formers and showed poor anti-blocking.
• Example 15 Making powder free latex gloves with a polymer formulation A formulated coagulant containing, 4% calcium chloride, 2% polymer from example 1 , 0.25% PMMA beads, and 0.1% SURFYNOL-465 surfactant was prepared. This dispersion was used as a release agent in the preparation of powder free latex gloves, using Method B. Compared to examples 3 & 4, the glove is more uniform, and easier to strip off the former. The glove also exhibited excellent anti-blocking.
• Emulsions were made according to Example 1 , where all compositions and procedures were kept the same except the temperature for adding the surfactants was varied. Table 5 lists the emulsion particle sizes, measured using a BI90 particle size analyzer, with respect to surfactant adding temperature. Table 5
• Emulsions were made according to Example 1 , where the salinity of the water was controlled by adding certain parts of sodium chloride into deionized water. All other compositions and procedures were kept the same. Table 6 lists the emulsion particle sizes, measured with a BI90 particle size analyzer, with respect to salt concentration in water.
• the gloves made with the emulsion having a particle size of 0.202 ⁇ m, and
• the emulsion polymers from example 18 were used as release agents in the preparation of powder free latex gloves, using Method B at 3% polymer concentration.
• the anti-blocking of the gloves was very good for gloves made with the emulsion having a particle size of 0.278 ⁇ m and acceptable for gloves
• Example 20 Coagulant resistance of emulsions with different particle size
• Example 17 1 part of the emulsion polymers of Example 17 was mixed with 3 parts of 5% calcium chloride solution.
• the emulsion having a particle size of 0.202 ⁇ m did not gel and the mixture was stable for weeks, and the emulsion having a particle size of 0.325 ⁇ m did not gel and the mixture showed slight settling after 3 days.

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• Paints Or Removers (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
• Moulds For Moulding Plastics Or The Like (AREA)
• Moulding By Coating Moulds (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2002
  • 2002-01-24 JP JP2002567512A patent/JP2004523389A/ja active Pending
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  • 2002-01-24 WO PCT/US2002/002219 patent/WO2002068168A2/en active Application Filing
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