CN1568342A - Mold release and anti-blocking coating for powder-free natural or synthetic rubber articles - Google Patents
Mold release and anti-blocking coating for powder-free natural or synthetic rubber articles Download PDFInfo
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- CN1568342A CN1568342A CN 02808283 CN02808283A CN1568342A CN 1568342 A CN1568342 A CN 1568342A CN 02808283 CN02808283 CN 02808283 CN 02808283 A CN02808283 A CN 02808283A CN 1568342 A CN1568342 A CN 1568342A
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- release compositions
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- 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
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- 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
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- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Gloves (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Paints Or Removers (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Moulding By Coating Moulds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention is directed to a release composition for molds and formers used in the production of natural and synthetic latex articles. The release coating contains a water-borne, high Tg polymer formed from at least one hydrophobic monomer and at least one hydrophilic monomer, where the Tg of the polymer is at least - 10 DEG C. One advantage of the release composition is that it is compatible with a coagulant solution used in the formation of latex gloves. Articles formed using the release coating have good anti-blocking properties.
Description
Technical field
The application is the part continuation application of pending application sequence number 09/790,093.
The present invention relates to be used to produce natural a kind of polymkeric substance mold release compositions and the used mould of synthetic rubber articles.This polymkeric substance mold release compositions is particularly useful for the moulding latex glove, can also prevent the adhesion of this class outer surface of glove.The advantage of mold release compositions of the present invention is to wash down from mould easily, and with present many manufacture method in used condensing agent compatible, so just cancelled the additional step that will on mould, be coated with release coating.
Background technology
As used herein, term latex glove or latex product are meant by gloves or goods natural or that synthetic rubber is made.By goods natural or that synthetic rubber is made is the resilient material with lower glass transition temperatures.The surfaces of tacky of these materials also tends to stick to each other.For example, when manufacturing processed finished, latex glove was difficult to from the glove mould the demoulding and gets off, and in the packing distribution when selling, they tend to bond together or lump.
There is several method to address this problem at present.A kind of method relates to uses particulate material or powder, as starch, and talcum powder or lime carbonate.But coagulant solution is advanced in the particle blend, so that form a barrier layer between latex and die surface.Powder helps gloves demoulding from the mould and gets off, can also anti-stick.Regrettably, powder-type coating is a kind of known public hazards, because loose powdered can float in air.Starch tends to absorb the protein in the natural rubber latex, and in use this powder deposits easily, and the pollution surrounding environment also causes anaphylaxis and other negative effects.In addition, protein/powdered compound is the grain of bacterium, can promote their procreations to grow.Recently, to growing without the demand of the powder-free natural rubber of loose powder and synthetic rubber gloves.
Another kind method is to provide necessary non-stick property with chlorination process, and as U.S. Patent number 4,851,266 is described.In this case, with lime carbonate as releasing agent and before chlorination flush away.Though this method can reduce the viscosity and the rubbing effect of rubber, it can reduce the kindliness of rubber and shorten the storage life of rubber item.And chlorination makes goods very smooth, thereby has worn the chlorination gloves and just be difficult to handle article.For addressing this problem, the chlorination glove surface often has decorative pattern.
Another method is to use silicone compositions.This class material helps gloves demolding, also can reduce viscosity.Regrettably, be when preparing in the next dip-coating cycle, the resistates of this material is difficult to wash down from mould.
The no talcum powder releasing agent that uses tensio-active agent is at U.S. Patent number 4,310, and is existing described in 928.
The polymkeric substance releasing agent also has been disclosed in this area.EP0640623 has described the chloroprene rubber of preparation, U.S. Patent number 5,534, and 350 have described polyurethane dispersions and U.S. Patent number 5,993,923; 5,691,069; 5,700,585; With 5,712,346 have described the phenylethylene ethylene/propenoic acid ester that contains siloxanes.The unsettled U.S. Patent application of submitting in unsettled U.S. Patent application 09/400,488 and on September 15th, 2000 has been described with the undercoat of star polymer as latex glove.
Be surprised to find that already, a kind of mold release compositions that contains the moisture high-tg polymer that forms by at least a hydrophobic monomer and at least a hydrophilic monomer, a kind of no powder release agent is provided, the non-stick property of finished product is provided, and helped on mould, to provide one deck slick latex settling.In addition, this mold release compositions can be dispersed in the polyelectrolyte condensing agent, thereby compatible with present popular manufacturing process.
Summary of the invention
Target of the present invention is a kind of mould that is applicable to natural or synthetic rubber articles, there is one deck mold release compositions on its surface, said composition comprises a kind of aqueous polymers that is formed by at least a hydrophobic monomer and at least a hydrophilic monomer, and the Tg of this polymkeric substance is at least-10 ℃.
Other embodiment of the present invention is to make the method for latex glove, wherein on mould, be coated with a kind of mold release compositions as release coating, said composition contains a kind of aqueous polymers that is formed by at least a hydrophobic monomer and at least a hydrophilic monomer, and its Tg is at least-10 ℃.
Another embodiment of the present invention is a kind of natural or synthetic rubber articles of surperficial band coating, and this coating comprises a kind of polymkeric substance that is formed by a kind of hydrophobic monomer and a kind of hydrophilic monomer, and its Tg is at least-10 ℃.
Another embodiment of the present invention is the coagulant for rubber latex that is used for making the powder-free rubber goods, and it comprises a kind of mold release compositions, and said composition comprises a kind of polymkeric substance that is formed by a kind of hydrophobic monomer and a kind of hydrophilic monomer, and its Tg is at least-10 ℃.
Though do not wish to be bound to any specific theory, believe, to the desired key characteristic of releasing agent coating be: a kind of high-tg polymer, it can provide non-stick property; Easily wash down from mould; Has the wettability that obtains the required film of smooth latex deposition; Affinity with the latex surface; Can make the shaping mould goods have non-stick property.
Embodiment
Target of the present invention is to produce the mould or the model of natural or synthetic rubber articles, and there is one deck mold release compositions on its surface, and said composition comprises a kind of moisture high-tg polymer that is formed by at least a hydrophobic monomer and at least a hydrophilic monomer.
Natural and synthetic rubber articles, as used herein, be meant the goods of making from low Tg adhesive polymer material.The example of this class material includes, but not limited to isoprene-isobutylene rubber, natural latex rubber, polyvinyl chloride, chloroprene rubber, paracril, viton, styrene-butadiene copolymer, urethane or interpenetrating polymer networks emulsion polymer, or their combination.
Aqueous polymers of the present invention is a kind of aqueous polymers made from the method known in the art such as letex polymerization and suspension polymerization.
So-called high-tg polymer is meant that Tg is at least-10 ℃, and preferred 25-200 ℃ is preferred 40-150 ℃.The monomer that is suitable for forming polymkeric substance of the present invention is ethylenically unsaturated monomers or their mixture.The hydrophobic monomer of particularly suitable comprises (methyl) acrylate, vinyl acetate, ethene and vinylbenzene.A kind of preferred hydrophobic monomer is a vinylbenzene.
Polymkeric substance of the present invention also forms from hydrophilic monomer.Hydrophilic monomer exists with the 10-90% of polymer weight.The hydrophilic monomer that is suitable for comprises following monomer: ionic, as negatively charged ion, positively charged ion or amphiphilic ions monomer; Or have enough nonionic polar functionalities, and as hydroxyl or amido, thus the monomer of possess hydrophilic property.The monomeric example of this class comprises; but be not limited to Hydroxyethyl Acrylate, vinyl cyanide, (methyl) vinylformic acid 2-(dimethylamino) ethyl ester, chlorination [3-(methacryloyl amino) propyl group] trimethyl ammonium, 2-acrylamido-2-methyl isophthalic acid-propanesulfonic acid sodium salt (a.k.a.AMPS), chlorination [2-(acryloxy) ethyl] trimethyl ammonium.Preferred hydrophilic monomer is vinylformic acid and methacrylic acid.
Polymkeric substance can randomly contain a kind of linking agent.The amount of linking agent is the 0-10% of polymer weight, preferred 0.5-5%.Preferred linking agent is a kind of two functionality linking agents, as Vinylstyrene, toxilic acid diallyl ester, Ethylene glycol dimethacrylate, Vinyl crotonate and diallyl phthalate.Also can use the polyfunctionality linking agent, as allyl group or vinyl sucrose ether, four (methyl) vinylformic acid pentaerythritol ester and trihydroxymethylpropanyl ester three (methyl) vinylformic acid or the like.
The average particle size particle size of emulsion polymer of the present invention, as measuring with photon correlation energy spectral technology, in the 0.05-1.5 mu m range, preferred 0.15-0.9 μ m, most preferably 0.2-0.6 μ m.Particle size can be regulated with the method known in the art, for example polymkeric substance inoculation, initiator concentration, control salt concn, the water hardness, surfactant concentration, surfactant types, or lean on temperature that tensio-active agent solubleness and the influence of drawing branch agent rate of decomposition are regulated.Have found that the particle size of emulsion polymer is crucial to suitable non-stick property.Particle size is also very important to anticoagulant.Too little particle anticoagulant deficiency, and too big particle can sedimentation in the condensing agent dilute solution.
Mold release compositions can randomly contain other composition, as dispersion agent, tensio-active agent, microballon and rheology modifier.
Be applicable to that tensio-active agent of the present invention comprises, but be not limited to, anionic, cationic, non-ionic type and amphiphilic ions type tensio-active agent; And polymeric surfactant, include but not limited to linear and radial copolymer.Tensio-active agent can improve the sedimentary homogeneity of latex, and the easier demoulding also improves the wettability of latex to the band coating mould.
Preferred release coating does not contain siloxanes, but add siloxanes in composition advantage is arranged also.Containing the problem that silicon compound brings in mold release compositions is that they can be stayed on the mould, make the more difficult cleaning of mould.
Mold release compositions also can contain microballon.Microballon can be used to reduce surperficial contact area, thereby reduces the cohesiveness between band coating rubber item and mould or other object.This can improve release property and non-stick property simultaneously.The diameter of microballon is less than 60 μ m, preferred 5-40 μ m, most preferably 10-30 μ m.Microballon can be by the harder any material manufacturing of analogy coated article.Be applicable to that microballon of the present invention is those that made by following polymers: the polymeric amide of nylon and so on, polymethylmethacrylate, polystyrene, polyethylene, polypropylene, tetrafluoroethylene, polyester, polyethers, polysulfones, polycarbonate, polyether-ether-ketone and other polymkeric substance and multipolymer, silicon-dioxide and Microcrystalline Cellulose.The preferred amount of microballon in mold release compositions is 0.05-5 weight %, most preferably 0.1-1 weight %.
Be dispersed in the moisture mold release compositions for helping microballon, can randomly add dispersion agent.Be applicable to that dispersion agent of the present invention includes, but not limited to tensio-active agent and polymeric dispersant, comprise the linear and radial copolymer of amphiphilic.
In mold release compositions, can randomly there be rheology modifier.Rheology modifier is used for the viscosity of control combination thing, for use in different manufacturing process and the equipment and the homogeneity and the thickness of control coating.Be applicable to that rheology modifier of the present invention includes, but not limited to Mierocrystalline cellulose, as Natvosol; Sun is from Natvosol such as polyquaternary amine-4 and Onamer M 0; The Natvosol of hydrophobically modified, carboxymethyl cellulose, methylcellulose gum and hydroxypropylcellulose; Starch that disperses or dissolves or treated starch; And glycan glue, as xanthan gum, guar gum, cationic guar gum such as chlorination melon ear hydroxypropyl three ammoniums and perverse locust bean gum.Other rheology modifier that is suitable for includes, but not limited to solubility in acid multipolymer, tensio-active agent etc.The add-on of rheology modifier is generally the 0.01-10 weight % of mold release compositions, preferred 0.02-3 weight %.
Mold release compositions also can contain other additive known in the art, for example tackifier, linking agent, biocides, low surface energy compounds, filler and suds suppressor.
The manufacture method of mold release compositions of the present invention is with the method known in the art each combination of components to be become aqueous dispersion.
The polymkeric substance release coating can be used to be coated with many materials that are used as the mould of natural and synthetic rubber articles.Mould can be any material known in the art, includes, but not limited to pottery, glass and stainless steel.Goods in die for molding comprise gloves, prevention device, conduit, tire, bathing cap, balloon, tubing and sheet material.A kind of specially suitable final application is the production that is used for latex glove as mold release compositions, comprises surgical glove, internal medicine latex examination gloves and workman's gloves, does not more particularly have the powder latex glove.
When being used for being coated with the mould of making gloves, can be with several diverse ways coated polymeric coating compositions.For example, in a kind of method of coating glove mould, the mould immersion with hand shape be contained in the solution or dispersion of mold release compositions, and then immersion contains in the coagulating agent mixture of latex.The condensing agent that is suitable for includes, but not limited to nitrocalcite and calcium chloride.In another approach, the hand shape mould immersion with cleaning contains in the condensing agent of mold release compositions.After the drying, just can the method known in the art make gloves with the mould of this band release coating and condensing agent coating.For example, the band coating mould is soaked for some time in natural or synthetic rubber latex, will be enough to the rubber coating that rubber is condensed and form desired thickness during this period of time.Then, these gloves of water leaching randomly are to remove the impurity in the rubber.Solidify molded gloves then in stove, cooling is also immersed in the coating composition, and the latter will become the undercoat of gloves.Perhaps also molded gloves can be immersed earlier in the coating composition, in stove, solidify then and cooling.Inner surface treatment includes, but not limited to known in the art those, comprises those polymkeric substance, other polymer coating, chlorination and starch described in Application No. 09/663,468 or clay powder interior, and above-mentioned patent is included in that this is for reference.After the cooling, gloves be taken off simultaneously from mould and turn over.Part or all of releasing agent on glove mould just is transformed into outer surface of glove like this.
Mold release compositions and condensing agent can be combined in same solution or the dispersion.Mold release compositions of the present invention is compatible with producing condensing agent used in the rubber item at present.Condensing agent and mold release compositions are made up in same processing step, just can make the producer in the technology of current popular, use this mold release compositions and need not expensive modification or additional other processing step.
Except the external coating (EC) that can be used as gloves, polymer composition of the present invention also should be made other industrial releasing agent, includes, but are not limited to: in the manufacturing of injection moulding, C-V joint and tire, synthetic gloves and other rubber item.
Goods with the moulding of mold release compositions of the present invention institute have good non-stick property.This performance prevents between latex glove, to stick together between the goods packaging together but that use after the separate easily each other.
For further specifying and explain the present invention, provided following examples, but must not be used as restriction to them.
Method A-makes latex glove with the pre-treatment mould
Latex glove can prepare as follows:
(a) a gloves forming mould is immersed in the solution or dispersion that comprises a kind of mold release compositions, to produce a band coating mould, described composition comprises a kind of Tg and is higher than-10 ℃ of aqueous polymers, and this polymkeric substance is formed by at least a hydrophobic monomer and at least a hydrophilic monomer;
(b) after the drying, this band coating mould is immersed in the conventional coagulant solution;
(c) described band coating mould is immersed natural rubber latex, on mould, to be coated with the above latex;
(d) randomly, leaching should be with the mould of latex coating in water, to remove the impurity in the rubber;
(e) will immerse the internal surface coating composition with the mould of latex coating;
(f) in stove, solidify this latex; And
(g) take off the finished product gloves from mould.
Method B one usefulness prescription condensing agent is made latex glove
Latex glove can prepare as follows:
(a) a gloves forming mould immersion is contained in a kind of coagulant solution of mold release compositions, to produce a band coating mould, described composition comprises the aqueous polymers that a kind of Tg that is formed by at least a hydrophobic monomer and at least a hydrophilic monomer is higher than-10 ℃;
(b) described band coating mould is immersed the natural rubber latex Ruzhong, on mould, to be coated with the above latex.
(c) randomly, leaching should be with the mould of latex coating in water, to remove the impurity in the rubber;
(d) will immerse with the mould of latex coating in the internal surface coating composition;
(e) in stove, solidify this latex; And
(f) take off the finished product gloves from mould.
The preparation of embodiment 1-emulsion polymer
Be equipped with mechanical stirrer, nitrogen inlet, thermometer and 2 to add entry (391g), TOMADOL 1-3 (13.8g) and LUBRHOPHOS LB-400 (8.6g) in the resin kettle of feeder at a slow speed at one.This is stirred the mixture is heated to 65 ℃, logical simultaneously nitrogen purge.Add 5% well-mixed pre-emulsion in this mixture, the preparation method of pre-emulsion is as follows: the vinylbenzene (83.5g), methacrylic acid (MAA) that slowly adds premix in the stirring premixed solution of LUBRHOPHOS LB-400 (8.6g), TOMADOL1-3 (13.8g) and water (216g) (177.5g) and Ethylene glycol dimethacrylate (2.4g).After reinforced the finishing, in this reaction vessel, add again and cause catalyzer Sodium Persulfate (0.2g is in 16.8g water), in the 30min this reaction mixture is being heated to 80 ℃ subsequently then.In case temperature of reaction reaches 80 ℃, will in 180min, add reaction mixture simultaneously and in 210min, add Sodium Persulfate solution (0.27g is in 60g water).After catalyzer adds, add tert-butyl peroxide (1.2g is in 2g water) immediately to remove residual monomer, behind 30min, add ferrous ammonium sulphate (0.3g is dissolved in 2% solution in the 5g water) then, in 30min subsequently, slowly add saccharosonic acid (1.2g is in 10g water) again.Cool off this reaction mixture then, filter by 80 order strainers, not purified can being used for fills a prescription.
This emulsion product contains 30% solid, and 68 parts of MAA, 32 parts of vinylbenzene and 1 part of linking agent are wherein arranged.The Tg that records this polymkeric substance with the MSI simulation software is 115 ℃.
Embodiment 2-contains the preparation of condensing agent polymkeric substance
In one 2 gallon container, add the polymers soln that 500g derives from embodiment 1.Slowly add 4500g coagulant solution (containing 10% nitrocalcite or 5% calcium chloride) then while stirring.This polymkeric substance is stable in the condensing agent dispersion, but can observe moderate throwing out.Can observe a little sediment gradually, but be easy to disperse again.This polymkeric substance that contains condensing agent can be kept several weeks and not change its performance.
Embodiment 3-usefulness method B prepares no powder gloves
The ceramic die of a cleaning of drip washing and 70 ℃ of oven dry.Then, soak 10-20s containing in the condensing agent polymkeric substance in deriving from embodiment 2 immediately.Allow this band coating mould part dry and in the room temperature caoutchouc latex, soak 20-30s then.Solidify a little (120 ℃/2min) after, with 60 ℃ of water leaching latex settlings, to remove the impurity in the natural rubber.Dry the filterable latex settling of this drop then and immerse in the polymkeric substance inner surface treatment solution, with coating internal surfaces.The gloves that this polymer treatment is crossed are at 90-130 ℃ of sulfuration 15-30min then.
This latex glove is easy to take off from mould.The latex glove that this 2 faces all pass through polymer treatment is no powder, and its internal surface has good wearable property and outside surface has non-stick property and non-slip gripability.
Then mould is immersed 1M KOH alkaline solution and use water wash, to remove residual polymkeric substance.Cleaned mould is used for new latex deposition.
Embodiment 4-usefulness method A makes no powder gloves
The ceramic die of a cleaning of drip washing and 70 ℃ of oven dry.Then, derive from polymer solids/water dispersion of embodiment 1 3% immediately and soak 10-20s.Then this mould is dried by the fire 1-4min at 70 ℃, and in conventional coagulant (10% nitrocalcite or 5% calcium chloride water), soak 10-20s.Then this band coating mould part is dried, and in the room temperature natural rubber latex, soak 20-30s.Solidify a little (120 ℃/2min) after, with this latex settling of 60 ℃ of water leachings, to remove the impurity in the natural rubber.Dry the filterable latex settling of this drop then, immerse polymkeric substance inner surface treatment solution again, with coating internal surfaces.The gloves that this polymer treatment is crossed are at 90 ℃-130 ℃ sulfuration 15-30min then.
This latex glove is easy to take off from mould.The latex glove that this 2 faces are all crossed through polymer treatment is no powder, and internal surface has good wearable property and outside surface has non-stick property and non-slip gripability.
Cleaning die then, method is: mould is immersed 1M KOH alkaline solution and uses water wash, to remove residual polymkeric substance.Cleaned mould is used for new latex deposition, can not reduce the gloves quality.
Embodiment 5-prepares no powder latex glove with the emulsion polymer with different Tg
Change monomer and form, prepare the emulsion polymer of different Tg by the method for embodiment 1.All polymkeric substance all contain 100 parts of monomers (pphm): 1 part of two functionality linking agent.
Table 1
| ?MAA | Vinylbenzene | Butyl acrylate | Estimate *Tg | |
| Sample 5A | ?68％ | ?32％ | 115℃ | |
| Sample 5B | ?35％ | ?40％ | 25％ | 74℃ |
| Sample 5C | ?35％ | ?25％ | 40％ | 53℃ |
*All Tg use the MSI simulation software to calculate.
As releasing agent,, under 3% polymer concentration, prepare no powder latex glove with above-mentioned polymkeric substance with method B.For all polymkeric substance, the latex settling is even, and after the demoulding, mould is easy to clean.About non-stick property, polymkeric substance 5A's is very good, and polymkeric substance 5B's is good, and polymkeric substance 5C's is general.
Embodiment 6-prepares no powder gloves with the different emulsion polymer of cross-linking density
With different linking agent (Ethylene glycol dimethacrylate) consumption, prepare emulsion polymer by the method for embodiment 1.The linking agent that per 100 parts of monomers (pphm) cooperate does not wait up to 5pphm from 0pphm, 0.5pphm, 1pphm, 2pphm, 3pphm, 4pphm.When dosage of crosslinking agent is 5pphm, observe gel phenomenon.These polymkeric substance, except contain the 5pphm linking agent, all be used as releasing agent, with method B, under 3% polymer concentration the preparation no powder latex glove.All polymkeric substance all form uniform latex settling, and mould is easy to clean after the demoulding.The release property of 0pphm linking agent and non-stick property reduce.All other polymkeric substance all show good non-stick property and release property.The demoulding especially easily when linking agent is 4pphm.
Embodiment 7-prepares no powder gloves with the different emulsion polymer of acid amount
With different acid amounts, prepare emulsion polymer by the method for embodiment 1.All polymkeric substance all contain 1pphm Ethylene glycol dimethacrylate linking agent.
Table 2
| ?MAA，％ | Vinylbenzene, % | |
| Sample 7A | ?0 | ?100 |
| Sample 7B | ?5 | ?95 |
| Sample 7C | ?20 | ?80 |
| Sample 7D | ?25 | ?75 |
| Sample 7E | ?35 | ?65 |
| Sample 7F | ?38 | ?62 |
| Sample 7G | ?48 | ?52 |
| Sample 7H | ?50 | ?50 |
| Sample 7I | ?68 | ?32 |
| Sample 7J | ?74 | ?26 |
| Sample 7K | ?80 | ?20 |
MAA is 80% reaction generation gel.Above-mentioned polymkeric substance, except that contain 80%MAA, all be used as releasing agent, with method B, under 3% polymer concentration the preparation no powder latex glove.0% and 5%MAA show good non-stick property and release property.Other all shows extraordinary non-stick property and release property.Polymkeric substance 7D has permanent stability in coagulating agent mixture.
Embodiment 8-does not have powder latex hand with the emulsion polymer manufacturing that contains methyl methacrylate (MMA)
Cover
Replace vinylbenzene with methyl methacrylate (MMA), prepare polymer emulsion by the method for embodiment 1.All polymkeric substance all contain 1pphm Ethylene glycol dimethacrylate linking agent.
Table 3
| ?MMA | ?MAA | |
| Sample 8A | ?32％ | 68％ |
| Sample 8B | ?50％ | 50％ |
| Sample 8C | ?75％ | 25％ |
As releasing agent,, under 3% polymer concentration, prepare no powder latex glove with above-mentioned polymkeric substance with method B.The result shows that the percentage ratio of methyl methacrylate is big more, and then release property and non-stick property are good more.All polymkeric substance have all provided qualified release property and non-stick property.
Embodiment 9-does not have the powder latex glove with the emulsion polymer manufacturing that contains other hydrophobic monomer
Replace vinylbenzene with other hydrophobic monomer, prepare polymer emulsion (table 4) by the method for embodiment 1.
Table 4
| Hydrophobic monomer | MAA | |
| Sample 9A | CHM32％ | 68％ |
| Sample 9B | IBXM75％ | 25％ |
| Sample 9C | DPA75％ | 25％ |
The monomer of polymkeric substance 9A-C comprises cyclohexyl methacrylate (CHM), isobornyl methacrylate (IBXM) and vinylformic acid two ring pentyl esters (DPA).All polymkeric substance all contain 1pphm two functionality linking agents.As releasing agent,, under 3% polymer concentration, make no powder latex glove with these polymkeric substance with method B.All samples has all provided qualified non-stick property and release property.
Embodiment 10-does not have the powder latex glove with the tensio-active agent manufacturing
Use a series of nonionic surface active agent, comprise the BRIJ of ICI company and the SURFYNOL of TWEEN and Air Products company, as releasing agent, with the no powder latex glove of method B preparation.Surfactant concentrations is 2% in the release coating.The latex settling is even, and mould is very easy to clean after the demoulding.Latex glove is easy to the demoulding, but shows bad non-stick property.
Embodiment 11-prepares no powder gloves with microballon
Polymethylmethacrylate (PMMA) microballon of the about 20 μ m of particle size is dispersed in the conventional coagulant solution (contains 10% nitrocalcite or 5% calcium chloride).The weight % of microballon in whole solution is 3%.Prepare no powder latex glove as releasing agent with method B with this dispersion.Latex glove is difficult to the demoulding.
Embodiment 12-prepares no powder latex glove with thickening material
Xanthan gum is dissolved in the conventional coagulant solution that contains 10% nitrocalcite or 5% calcium chloride.The concentration of xanthan gum in the preparation condensing agent is 0.04%.As releasing agent, prepare no powder latex glove with this dispersion with method B.This latex glove is difficult to the demoulding and shows bad non-stick property.
Embodiment 13-prepares no powder latex glove with polymkeric substance and thickening material
Preparation contains the prescription condensing agent that 0.04% xanthan gum and 3% derives from the polymkeric substance of embodiment 1.As releasing agent, prepare no powder latex glove with this dispersion with method B.The polymeric coating of appearance is more even than embodiment's 3.
Embodiment 14-prepares no powder latex glove with microballon, tensio-active agent and thickening material
Preparation contains 0.3% microballon, 0.1%SURFYNOL-465 and 4%CaCl
2The prescription condensing agent.As releasing agent, prepare no powder latex glove with this dispersion with method B.External coating (EC) is even, but latex glove is difficult to the demoulding and shows bad non-stick property.
Embodiment 15-prepares no powder latex glove with polymer formulators
Preparation contains the prescription condensing agent of polymkeric substance, 0.25%PMMA microballon and 0.1%SURFYNOL-465 tensio-active agent that 4% calcium chloride, 2% derives from embodiment 1.As releasing agent, prepare no powder latex glove with this dispersion with method B.Compare with 4 with embodiment 3, this gloves are more even, the easier demoulding.This gloves also show good non-stick property.
Embodiment 16-particle size is measured
With BI90 grain size analysis instrument, at 25 ℃, the particle size that records the emulsion polymer that derives from embodiment 1 with the photon correlation spectroscopic technique is 0.24 μ m.
Embodiment-17 is by temperature of reaction control particle size
Method according to embodiment 1 prepares emulsion, and wherein all compositions all keep identical with step, but changes the temperature that adds tensio-active agent.Table 5 has been listed the relation that the emulsion particle size that records with BI90 grain size analysis instrument and tensio-active agent add temperature.
Table 5
| Sample | Tensio-active agent adds temperature | Particle size |
| 17A | 80℃ | 0.325μm |
| 17B | 60℃ | 0.202μm |
| 17C | 20℃ | 0.103μm |
Embodiment 18-is by salt concn control particle size
Method according to embodiment 1 prepares emulsion, wherein controls the salt concn of water by the sodium-chlor that adds certain umber in deionized water.All other compositions all keep identical with step.Table 6 has been listed the relation of salt concn in the emulsion particle size that records with BI90 grain size analysis instrument and the water.
Table 6
| Sample | Salt concn | Particle size |
| 18A | ?100ppm | ?0.162μm |
| 18B | ?1000ppm | ?0.278μm |
| 18C | ?10,000ppm | Reaction gelization |
The non-stick property of the emulsion that embodiment 19-particle size is different
With emulsion polymer that derives from embodiment 17 and particle size be the emulsion polymer of 0.58 μ m as releasing agent, with method B, under 3% polymer concentration, make no powder latex glove.With particle size is that the gloves that the emulsion of 0.58 μ m and 0.325 μ m is made have extraordinary non-stick property, with particle size is that the gloves non-stick property made of the emulsion of 0.202 μ m is good, and is that the gloves non-stick property made of the emulsion of 0.103 μ m is bad with particle size.
As releasing agent, under 3% polymer concentration, make no powder latex glove with the emulsion polymer that derives from embodiment 18 with method B.With particle size is that the gloves that the emulsion of 0.278 μ m is made have extraordinary non-stick property, is that the gloves non-stick property made of the emulsion of 0.162 μ m is qualified by particle size.
The anticoagulant of the emulsion that embodiment 20-particle size is different
Emulsion polymer among 1 part of embodiment 17 is mixed with 3 part of 5% calcium chloride solution.Particle size is the emulsion generation gelation of 0.103 μ m, particle size is the not gelation of emulsion of 0.202 μ m, and this mixture is stable in several weeks, and particle size is the not gelation of emulsion of 0.325 μ m, but this mixture precipitation slightly after 3 days.
Claims (24)
1. a mould or model of producing natural or synthetic rubber articles, there is one deck mold release compositions on its surface, and said composition comprises a kind of moisture high-tg polymer, and this polymkeric substance is formed by following component:
(1) at least a hydrophobic monomer; With
(2) at least a hydrophilic monomer,
The Tg of wherein said aqueous polymers is at least-10 ℃.
2. the mould of claim 1 or model, wherein said aqueous polymers comprises a kind of emulsion polymer.
3. the mould of claim 2 or model, the particle size of wherein said aqueous polymers is 0.05-1.5 μ m.
4. the mould of claim 3 or model, the particle size of wherein said aqueous polymers is 0.15-0.9 μ m.
5. the mould of claim 1 or model, wherein said hydrophobic monomer comprises vinylbenzene.
6. the mould of claim 1 or model, wherein said hydrophilic monomer is a kind of acid mono.
7. the mould of claim 1 or model, wherein said mold release compositions also comprises a kind of tensio-active agent.
8. the mould of claim 1 or model, wherein said mold release compositions also comprises microballon.
9. the mould of claim 1 or model, wherein said mold release compositions also comprises a kind of dispersion agent.
10. the mould of claim 1 or model, wherein said aqueous polymers also comprises a kind of linking agent.
11. the mould of claim 1 or model, wherein said mold release compositions also comprises a kind of rheology modifier.
12. the mould of claim 1 or model, wherein said mold release compositions also comprises a kind of condensing agent.
13. the mould of claim 1 or model, wherein said high-tg polymer comprises:
A) 20-35 weight % methacrylic acid;
B) 65-80 weight % vinylbenzene; With
C) 0.5-1.5 weight % linking agent.
14. the mould of claim 1 or model, wherein said mold release compositions is silicon-containing compound not.
15. one kind comprises goods natural or synthetic rubber moulding product, and coating composition is arranged on it, said composition comprises a kind of moisture high-tg polymer, and this polymkeric substance is formed by following component:
(1) at least a hydrophobic monomer; With
(2) at least a hydrophilic monomer,
The Tg of wherein said aqueous polymers is at least-10 ℃.
14. the goods of claim 12, wherein said goods do not contain powder.
15. a method of making gloves, it comprises:
(a) the glove mould immersion is contained in the coagulant solution of mold release compositions, to form the band coating mould, described mold release compositions comprises the aqueous polymers that a kind of Tg is at least-10 ℃, and this polymkeric substance is formed by at least a hydrophobic monomer and at least a hydrophilic monomer;
(b) described band coating mould is immersed the natural rubber latex Ruzhong, with the described latex of coating on this mould;
(c) will immerse with the mould of latex coating in the internal surface coating composition;
(d) in stove, solidify this latex; And
(e) take off the finished product gloves from mould.
16. the method for claim 14, wherein step (a) comprises two discrete steps:
A.1) described ceramic die is immersed in the described aqueous polymers mold release compositions; With
A.2) will immerse in the coagulant solution with the ceramic die of release coating.
17. the method for claim 14, the band latex coating mold of wherein said step (b) will be in step (c) leaching in water earlier before.
18. a mold release compositions, it comprises:
A) a kind of moisture high-tg polymer that forms by at least a hydrophobic monomer and at least a hydrophilic monomer, the Tg of wherein said aqueous polymers is at least-10 ℃;
B) a kind of condensing agent.
19. the composition of claim 17, wherein said condensing agent are a kind of calcium salts.
20. the composition of claim 17, it also comprises microballon.
21. the composition of claim 17, it also comprises a kind of rheology modifier.
22. the composition of claim 17, it also comprises a kind of tensio-active agent.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/790,093 | 2001-02-21 | ||
| US09/790,093 US20020155309A1 (en) | 2001-02-21 | 2001-02-21 | Mold release and anti-blocking coating for powder-free natural or synthetic rubber articles |
| US09/882,222 US6784397B2 (en) | 2001-02-21 | 2001-06-15 | Mold release and anti-blocking coating for powder-free natural of synthetic rubber articles |
| US09/882,222 | 2001-06-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1568342A true CN1568342A (en) | 2005-01-19 |
| CN1289577C CN1289577C (en) | 2006-12-13 |
Family
ID=27120994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02808283 Expired - Fee Related CN1289577C (en) | 2001-02-21 | 2002-01-24 | Mold release and anti-blocking coating for powder-free natural or synthetic rubber articles |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1373374A2 (en) |
| JP (1) | JP2004523389A (en) |
| CN (1) | CN1289577C (en) |
| WO (1) | WO2002068168A2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106366348A (en) * | 2016-08-30 | 2017-02-01 | 中广核达胜加速器技术有限公司 | Rubber irradiation aid |
| CN107151287A (en) * | 2017-05-24 | 2017-09-12 | 儒芯微电子材料（上海）有限公司 | A kind of crosslinking acrylate analog copolymer and its photoresist |
| CN110947305A (en) * | 2018-09-27 | 2020-04-03 | 北京铂阳顶荣光伏科技有限公司 | Hollow fiber membrane packaging method and hollow fiber membrane module |
| CN111016018A (en) * | 2019-12-18 | 2020-04-17 | 中交第二航务工程局有限公司 | Special external mold release agent for non-aqueous reaction type double-component foam polyurethane and preparation method thereof |
| CN113185887A (en) * | 2021-05-24 | 2021-07-30 | 山西吸睛科技有限公司 | Hydrophobic/hydrophilic polymer release agent and preparation method and application thereof |
| CN114854477A (en) * | 2022-04-27 | 2022-08-05 | 重庆渝江压铸有限公司 | Silicon-free mold release agent with excellent mold release performance and preparation method thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030175500A1 (en) * | 2002-03-18 | 2003-09-18 | Apala Mukherjee | Polymer coating for rubber articles |
| US7816446B2 (en) | 2004-10-01 | 2010-10-19 | Illinois Institute Of Technology | Interpenetrated rubber particles and compositions including the same |
| KR101606189B1 (en) * | 2008-08-27 | 2016-03-24 | 아벤트, 인크. | Thin, smooth nitrile rubber gloves |
| AU2009339262C1 (en) | 2009-02-05 | 2015-08-13 | Diptech Pte Limited | Production of elastomeric films |
| CN114276729A (en) * | 2020-09-17 | 2022-04-05 | 顶级手套国际有限公司 | Silicone-free polymer coating composition for coating elastomeric articles and method of preparing elastomeric articles coated therewith |
| CN115895768A (en) * | 2021-08-20 | 2023-04-04 | 南京瑞润新材料科技有限公司 | Demoulding composition for preparation process of medical latex gloves |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5712346A (en) * | 1995-02-14 | 1998-01-27 | Avery Dennison Corporation | Acrylic emulsion coatings |
| AU4920696A (en) * | 1995-02-14 | 1996-09-04 | Allegiance Corporation | A multiple dip process for making a powder-free article |
| JPH11507085A (en) * | 1995-02-14 | 1999-06-22 | エイベリ デニソン コーポレイション | Acrylic emulsion coating for rubber articles |
| AU781491B2 (en) * | 1999-04-14 | 2005-05-26 | Sumitomo Rubber Industries, Ltd. | Acrylic resin glove and internal surface treating agent thereof |
| ATE266697T1 (en) * | 1999-09-21 | 2004-05-15 | Nat Starch Chem Invest | USE OF A POLYMER COATING FOR RUBBER OBJECTS |
| US6692840B1 (en) * | 2000-09-15 | 2004-02-17 | National Starch And Chemical Investment Holding Corporation | Polymer coating for rubber articles |
-
2002
- 2002-01-24 EP EP02703237A patent/EP1373374A2/en not_active Withdrawn
- 2002-01-24 WO PCT/US2002/002219 patent/WO2002068168A2/en active Application Filing
- 2002-01-24 JP JP2002567512A patent/JP2004523389A/en active Pending
- 2002-01-24 CN CN 02808283 patent/CN1289577C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106366348A (en) * | 2016-08-30 | 2017-02-01 | 中广核达胜加速器技术有限公司 | Rubber irradiation aid |
| CN107151287A (en) * | 2017-05-24 | 2017-09-12 | 儒芯微电子材料（上海）有限公司 | A kind of crosslinking acrylate analog copolymer and its photoresist |
| CN107151287B (en) * | 2017-05-24 | 2020-06-02 | 儒芯微电子材料（上海）有限公司 | Cross-linked acrylate copolymer and photoresist thereof |
| CN110947305A (en) * | 2018-09-27 | 2020-04-03 | 北京铂阳顶荣光伏科技有限公司 | Hollow fiber membrane packaging method and hollow fiber membrane module |
| CN111016018A (en) * | 2019-12-18 | 2020-04-17 | 中交第二航务工程局有限公司 | Special external mold release agent for non-aqueous reaction type double-component foam polyurethane and preparation method thereof |
| CN113185887A (en) * | 2021-05-24 | 2021-07-30 | 山西吸睛科技有限公司 | Hydrophobic/hydrophilic polymer release agent and preparation method and application thereof |
| CN114854477A (en) * | 2022-04-27 | 2022-08-05 | 重庆渝江压铸有限公司 | Silicon-free mold release agent with excellent mold release performance and preparation method thereof |
| CN114854477B (en) * | 2022-04-27 | 2023-08-08 | 重庆渝江压铸有限公司 | Silicon-free release agent with excellent release performance and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1289577C (en) | 2006-12-13 |
| WO2002068168A3 (en) | 2003-02-27 |
| EP1373374A2 (en) | 2004-01-02 |
| JP2004523389A (en) | 2004-08-05 |
| WO2002068168A2 (en) | 2002-09-06 |
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