CN1439661A - Preparation for multicomponent/multiphase environment protecting latex gloves - Google Patents
Preparation for multicomponent/multiphase environment protecting latex gloves Download PDFInfo
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- CN1439661A CN1439661A CN 02110870 CN02110870A CN1439661A CN 1439661 A CN1439661 A CN 1439661A CN 02110870 CN02110870 CN 02110870 CN 02110870 A CN02110870 A CN 02110870A CN 1439661 A CN1439661 A CN 1439661A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
- C08G18/4241—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols from dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
Abstract
A "multi-component/multi-phase" green latex gloves is prepared from natural latex, synthetic latex, hybridized latex, or their compound through preparing the dispersed-in-water polyurethane solution from multi-component polyol, and compounding with conjugated vinyl diolefin, unsaturated carboxylic acid, other functional monomers and nano-class hybridized latex.
Description
The present invention is the preparation method of " many components/heterogeneous " green emgloves.
The greenization production of product, application and recovery are the trend of world today's development, meet the developing direction of advanced productivity, are the signs of civilization of human society.Latex and the growing application of goods thereof to low organic volatile (VOC) in national economy and the people's daily life have embodied the requirement that greenization develops just.
Natural rubber latex and synthetic latex goods are of a great variety, have been widely used in aspects such as daily life, health care, aerological sounding and electronic industry.The dipped goods of latex mainly contains surgery medical gloves, oxygen bag, catheter, tourniquet, condom, finger-stall, industrial gloves, domestic purpose gloves, insulating gloves, balloon etc.Latex glove is because its price is low, and the domestic purpose gloves of using from the operating glove to the handguard makes its application ubiquitous.Natural rubber latex and goods thereof are the main latex of using, but owing to caseic existence in the natural rubber latex, cause the allergy-contact rubella disease of skin easily, and easily produce offensive odour.Synthetic latex mainly contains neoprene, chlorobenzene, butyronitrile, butyl, urethane, acrylate and their blend and multipolymer etc., because these latex products can not cause allergic because of proteic existence, and oil resistant and chemical resistance are excellent, oxytolerant and ozonize, hyposmosis, penetration-resistant can be better than the natural rubber latex goods, and feel is the same with the natural rubber latex goods.Wherein neoprene and nitrile rubber and goods industrialization, but the pungent odours of the recycling of polychloroprene latex goods and nitrile rubber and goods thereof etc. have influenced applying of they again.The polyurethane rubber latex of being made up of polyurethane aqueous dispersion is a general orientation of researching and developing at present.The polyurethane adhesive milk-product have organic solvent-resistant and chemical, wear-resisting, good weatherability, and toughness and elasticity are excellent, and the recovery of polyurethane adhesive milk-product can be handled by degraded of biological and chemical method or burning method.But its wetting ability had both made it can be compound with itself or other latex dip-coating, also can bring the adhesion between goods.Therefore, giving full play to the advantage of urethane, avoid and overcome its weak point, is the key problem in technology of polyurethane rubber latex and goods research and development.
Natural rubber latex and synthetic latex and the existing report of goods research thereof, latex can form monofilm in composite back, also can form multilayer film by different latex.Day disclosure special permission bulletin 09310209 (1997) has reported that Deproteinization natural rubber latex and nitrile rubber are composite, and the latex glove that makes through dipping has the characteristic of not yellowing of oil resistant.Day disclosure special permission bulletin 11081014 (1999) and 200199112 (2000) has then been introduced and has been added colloid silica can improve anti-tear the drawing property of emgloves and the easy property shirked in natural rubber latex.Day disclosure special permission bulletin 08283522 (1996) has reported that sneaking into trade names in carboxylic acrylonitrile butadiene rubber latex can make dipped goods demonstrate good solvent-resisting and oil-proofness for the PAUR of " Hydran HW920 ".World patent WO9924507 has reported that the dipped goods rebound resilience of neoprene and the composite latex of butyronitrile is good, and does not have supersensitivity.Natural rubber latex has the performance of many excellences, as being covered with one deck synthetic latex again at the natural rubber latex product surface, then can overcome the supersensitivity of skin to the natural rubber latex goods.United States Patent (USP) 5,088 is coated on the natural emulsion gloves after 1225 (1992) the polyurethane aqueous dispersion mixing of having reported with different-grain diameter, can effectively reduce the supersensitivity of skin to natural rubber latex.United States Patent (USP) 5,985,955 (1999) have reported introducing the non-ionic hydrophilic polymkeric substance on the polyurethane chain and make after crosslinked and have cancellated hydrophilic polyurethane coating with the natural rubber latex goods are laminated with together, the emgloves of formation waterproof, anti-organic solvent.
The objective of the invention is by polyester and polyether Glycols and trivalent alcohol and contain the dibasic alcohol and the alicyclic polyisocyanates addition reaction of hydrophilic ionic group, behind neutralization, chain extension, make many components anionic polyurethane aqueous dispersions, dip forming is the polyurethane latex gloves behind the dispersible cross-linked resin of water but this water-based latex is sneaked into, after also can be composite with the hydridization latex of carboxyl butylbenzene, carboxyl butyronitrile, acrylate and nano silicon oxide, flood into emgloves, be used for fields such as daily life and health care.
Details are as follows in the present invention:
(1) the many components polyvalent alcohol in the polyurethane aqueous dispersion is made up of with the dibasic alcohol that contains hydrophilic (or ion) group with trivalent alcohol and their mixture polyester or polyether Glycols.Polyester polyol is made up of hexanodioic acid, neopentyl glycol, butyleneglycol, ethylene glycol, 3-hydroxymethyl-propane, and polyether glycol is made up of propylene oxide and propylene glycol, ethylene glycol.The molecular weight of polyester and polyether glycol is 150～5000, and desired molecular weight is 500～3500.When polyester mixed use with polyether glycol, both mix molar ratio can be from 5～100%, and desirable molar ratio is 8～50%.Self-emulsifying anionic polyurethane aqueous dispersions is owing to introduced ionic group carboxyl, sulfonic acid or sulfate radical in the molecular chain, the dibasic alcohol that contains hydrophilic radical (or ionic group) in many components polyvalent alcohol is used carboxylic dibasic alcohol always, as dimethylol propionic acid (DMP), its content is 0.5～20%, and desired contents is 2～12%.The polyisocyanates that forms urethane with polyol reaction has tolylene diisocyanate (TDI), 4,4 ,-methylenediphenyl diisocyanates (MDI), hexa-methylene and isocyanic ester (HDI) and isophorone diisocyanate (IPDI).According to emgloves outward appearance and performance demands, select for use aliphatics or alicyclic diisocyanate more satisfactory, i.e. HDI or IPDI.
(2) many components polyvalent alcohol and polyisocyanates addition reaction generate prepolymer, with in inorganic or the organic bases and after, behind the diamine chain extension, form polyurethane aqueous dispersion.The mineral alkali of neutralization usefulness is selected ammoniacal liquor (content is greater than 20%) for use, and organic bases is more satisfactory with triethylamine.Chain extension selects for use quadrol more satisfactory with diamine.The solid content of polyurethane aqueous dispersion is 20～50%, and desired contents is 25～40%, and the pH of aqueous dispersions is 7.0～9.0.For the performance that makes the polyurethane adhesive milk-product is more perfect, can be by in polyurethane aqueous dispersion, adding the dispersible cross-linked resin of entry, form the urethane crosslinks network with reactive hydrogen, carboxyl and hydroxyl reaction on the molecular chain and realize.But water decentralized crosslinking resin adopts 303 full methyl-etherified melamine resins of the special company of U.S.'s cyanogen, and add-on is 1～40%, and desirable consumption is 5～30%.
(3) homopolymer or the multipolymer with composite vinyl, conjugated diene and the unsaturated carboxylic acid of polyurethane aqueous dispersion and other functional monomer is the serial latex of BSN of selecting the total institute of blue star chemical science and technology for use with the hydridization latex that the inorganic nano material silicon oxide forms, and more satisfactory composite latex has urethane-carboxyl butylbenzene hydridization latex (BSN-1bs), urethane-carboxyl butyronitrile hydridization latex (BSN-1ban) and polyurethane-acrylate hydridization latex (BSN-1wq).Nano silicon oxide is dispersed in the gel-film, can play strengthening action.Polyurethane rubber latex and hydridization latex compound proportion are 1～99%, and desired proportions is 10～70%.Composite back latex stability improves, and institute's film forming properties is excellent.
(4) polyurethane aqueous dispersion or its composite latex are as the latex of green emgloves, with nitrocalcite type peptizer, utilize ionic depositing method, after ceramic hand-mold floods, through 60～170 ℃ of dryings, obtain green latex glove again in latex, its thickness is 0.05～0.5mm, ideal thickness is 0.08～0.16mm, and the tensile strength of film is greater than 5MPa, and elongation is greater than 500%.
Example one
In reaction flask, add 22.7 parts of PNPGA polyneopentyl glycol adipate, 2.3 parts of dimethylol propionic acids, 2.8 parts of N-Methyl pyrrolidone, 10 parts of isophorone diisocyanates, stir then, heat, 80～100 ℃ the reaction 5 hours after, be cooled to below 60 ℃, under high-speed stirring, add 55.6 parts of water, 1.9 parts of triethylamines again, obtain the aqueous dispersions of prepolymer, the pH that adds the polyurethane aqueous dispersion that obtains behind 0.34 part of quadrol chain extension is 7.7, solid content 35%, rotary viscosity is 57.5 centipoises under the room temperature.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～110 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 7.2MPa.
Example two
In reaction flask, add 22.6 parts of poly-hexanodioic acids, butyleneglycol, glycol ester, 1.7 parts of dimethylol propionic acids, 2.8 parts of N-Methyl pyrrolidone, 8.6 parts of isophorone diisocyanates, stir then, heat, 80～100 ℃ the reaction 5 hours after, be cooled to below 60 ℃, under high-speed stirring, add 53.2 parts of water, 1.4 parts of triethylamines again, obtain the aqueous dispersions of prepolymer, the pH that adds the polyurethane aqueous dispersion that obtains behind 0.33 part of quadrol chain extension is 7.0, solid content 35%, rotary viscosity is 16.4 centipoises under the room temperature.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～110 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 6.9MPa.
Example three
In reaction flask, add 24.8 parts of PNPGA polyneopentyl glycol adipate, 0.7 part of dimethylol propionic acid, 0.2 gram TriMethylolPropane(TMP), 3.1 parts of N-Methyl pyrrolidone, 8 parts of isophorone diisocyanates, stir then, heat, 80～100 ℃ the reaction 5 hours after, be cooled to below 60 ℃, under high-speed stirring, add 60.2 parts of water, 0.6 part of triethylamine again, obtain the aqueous dispersions of prepolymer, the pH that adds the polyurethane aqueous dispersion that obtains behind 0.7 part of quadrol chain extension is 7.5, solid content 35%, rotary viscosity is 18 centipoises under the room temperature.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～110 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 7.1MPa.
Example four
Under high-speed stirring, add 7 parts of full methyl-etherified trimeric cyanamides (303) in 100 parts of the polyurethane rubber latexs that obtains by example three, obtain the stable latex of oyster white.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～170 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 8.4MPa.
Example five
100 parts of the polyurethane rubber latexs that contains cross-linked resin that is obtained by example four mix for 20 parts with carboxyl butyronitrile/silicon oxide hydridization latex (BSN-ban), obtain the stable latex of oyster white.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～170 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 9.1MPa, film resilience is good.
Example six
100 parts of the polyurethane rubber latexs that contains cross-linked resin that is obtained by example four mix for 20 parts with carboxyl butylbenzene/silicon oxide hydridization latex (BSN-bs), obtain the stable latex of oyster white.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～170 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 9.3MPa, film resilience is good.
Example seven
100 parts of the polyurethane rubber latexs that contains cross-linked resin that is obtained by example four mix for 20 parts with acrylate/silicon oxide hydridization latex (BSN-1wq), obtain the stable latex of oyster white.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～170 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 8.9MPa, film resilience is good.
Example eight
In reaction flask, add 20.8 parts of poly-hexanodioic acids, butyleneglycol, glycol ester, 1.6 parts of poly(propylene oxide) trivalent alcohols, 0.6 part of dimethylol propionic acid, 4.2 parts of N-Methyl pyrrolidone, 6.1 parts of isophorone diisocyanates, stir then, heat, 80～100 ℃ the reaction 5 hours after, be cooled to below 60 ℃, under high-speed stirring, add 64.4 parts of water, 0.5 part of triethylamine again, obtain the aqueous dispersions of prepolymer, the pH that adds the polyurethane aqueous dispersion that obtains behind 0.5 part of quadrol chain extension is 7.8, solid content 30%, rotary viscosity is 17 centipoises under the room temperature.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～110 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 5.2MPa.
Example nine
Under high-speed stirring, add 5 parts of full methyl-etherified trimeric cyanamides (303) in 100 parts of the polyurethane rubber latexs that obtains by example eight, obtain the stable latex of oyster white.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～170 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 6.9MPa.
Example ten
100 parts of the polyurethane rubber latexs that contains cross-linked resin that is obtained by example nine mix for 20 parts with carboxyl butyronitrile/silicon oxide hydridization latex (BSN-ban), obtain the stable latex of oyster white.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～170 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 8.7MPa, film resilience is good.
Example 11
100 parts of the polyurethane rubber latexs that contains cross-linked resin that is obtained by example nine mix for 20 parts with carboxyl butylbenzene/silicon oxide hydridization latex (BSN-bs), obtain the stable latex of oyster white.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～170 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 8.7MPa, film resilience is good.
Example 12
100 parts of the polyurethane rubber latexs that contains cross-linked resin that is obtained by example nine mix for 20 parts with acrylate/silicon oxide hydridization latex (BSN-1wq), obtain the stable latex of oyster white.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～170 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 7.9MPa, film resilience is good.
Example 13
In reaction flask, add 25.2 parts of poly(propylene oxide) dibasic alcohol, 1.8 parts of dimethylol propionic acids, 0.2 part of TriMethylolPropane(TMP), 3.2 parts of N-Methyl pyrrolidone, 8.5 parts of isophorone diisocyanates, stir then, heat, 80～100 ℃ the reaction 5 hours after, be cooled to below 60 ℃, under high-speed stirring, add 56.2 parts of water, 1.5 parts of triethylamines again, obtain the aqueous dispersions of prepolymer, the pH that adds the polyurethane aqueous dispersion that obtains behind 0.2 part of quadrol chain extension is 7.6, solid content 35%, rotary viscosity is 95 centipoises under the room temperature.Under high-speed stirring, add 7 parts of full methyl-etherified trimeric cyanamides (303), obtain the stable latex of oyster white.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～110 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 6.1MPa.
Example 14
100 parts of the polyurethane rubber latexs that contains cross-linked resin that is obtained by example 13 mix for 20 parts with carboxyl butyronitrile/silicon oxide hydridization latex (BSN-ban), obtain the stable latex of oyster white.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～170 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 6.9MPa, film resilience is good.
Example 15
100 parts of the polyurethane rubber latexs that contains cross-linked resin that is obtained by example 13 mix for 20 parts with carboxyl butylbenzene/silicon oxide hydridization latex (BSN-bs), obtain the stable latex of oyster white.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～170 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 7.2MPa, film resilience is good.
Example 16
100 parts of the polyurethane rubber latexs that contains cross-linked resin that is obtained by example 13 mix for 20 parts with acrylate/silicon oxide hydridization latex (BSN-1wq), obtain the stable latex of oyster white.With nitrocalcite type peptizer, utilize ionic depositing method, in latex, behind the dipping, through 60～170 ℃ of dryings, obtain transparent latex glove again, 0.14 millimeter of thickness, 500% tensile modulus is 7.1MPa, film resilience is good.
Claims (21)
1. the preparation method of one kind " many components/heterogeneous " green emgloves, process is as follows:
(1) contains the preparation of the polyurethane aqueous dispersion of many components polyvalent alcohol;
(2) polyurethane aqueous dispersion and hydridization latex is composite;
(3) adopt the green emgloves of immersion process for preparing.
2. urethane according to claim 1 is meant that many components polyvalent alcohol and the compound addition reaction that contains vulcabond are after chain extension and forming.
3. the polyisocyanates in the urethane according to claim 1 is meant aliphatics or aromatic polyisocyanate, aliphatic polyisocyante can be a straight chain, it also can be cyclic, green gloves made of latex urethane is aliphatic polyisocyante preferably, as hexa-methylene and isocyanic ester (HDI) and isophorone diisocyanate (IPDI).
4. aqueous dispersions according to claim 1 is meant with water to be dispersion medium or with water and the dispersion medium formed with the molten organic solvent of water, usually with water as dispersion medium.
5. the solid content of the polyurethane aqueous dispersion of many components polyvalent alcohol according to claim 1 is 20～50%, and desired contents is 25～40%, and the pH of aqueous dispersions is 7.0～9.0.
6. the organic volatile of the polyurethane aqueous dispersion of many components polyvalent alcohol according to claim 1 (VOC) content is not more than 8%.
7. the polyurethane aqueous dispersion of many components polyvalent alcohol according to claim 1 is meant on macromolecular chain the self-emulsifying polyurethane system of introducing hydrophilic radical or ionic group and forming.
8. the polyurethane aqueous dispersion of many components polyvalent alcohol according to claim 1 is meant anionic self-emulsifying polyurethane system.
9. many components polyvalent alcohol according to claim 1 is meant the dibasic alcohol and the trivalent alcohol of polyester and polyethers and contains the mixture of hydrophilic radical (or ionic group) dibasic alcohol.
10. the polyester in many components polyvalent alcohol according to claim 9 can be from 5～100% with the molar ratio that mixes of the dibasic alcohol of polyethers and trivalent alcohol mixture, and desirable molar ratio is 8～50%.
11. the pure and mild trivalent alcohol of polyester binary in many components polyvalent alcohol according to claim 9 is made up of hexanodioic acid, neopentyl glycol, butyleneglycol, ethylene glycol, 3-hydroxymethyl-propane, polyether Glycols and trivalent alcohol are made up of propylene oxide and propylene glycol, ethylene glycol.
12. the molecular weight of the polyester in many components polyvalent alcohol according to claim 9 and the dibasic alcohol of polyethers and trivalent alcohol is 150～5000, desired molecular weight is 500～3500.
13. the dibasic alcohol content that contains hydrophilic radical (or ionic group) in many components polyvalent alcohol according to claim 9 is 0.5～20%, desired contents is 2～12%.
Has cancellated urethane to improve the rebound resilience of material 14. add the dispersible cross-linked resin formation of entry in the urethane according to claim 1, used cross-linked resin is the melamine resin of full methyl-etherified, add-on is 1～40%, and desirable consumption is 5～30%.
15. hydridization latex according to claim 1 is meant the nucleocapsid structure hybrid aqueous dispersions that a kind of organic polymer and inorganic nano material constitute, organic polymer is the homopolymer or the multipolymer of vinyl, conjugated diene and unsaturated carboxylic acid and other functional monomer, and inorganic nano material is nano oxidized silicon particle.
16. the organic polymer in hybridized glue according to claim 15 Ruzhong is carboxylic acrylonitrile butadiene rubber latex, carboxylic styrene butadiene latex and acrylic ester emulsion.
17. the compound proportion of polyurethane aqueous dispersion according to claim 1 and hydridization latex is 1～99%, desired proportions is 10～70%.
18. the composite latex stability of polyurethane aqueous dispersion according to claim 1 and hydridization latex is excellent, its scratch resistance, wear resistance, thermotolerance and mechanical property etc. all are improved after the film forming.
19. according to the described green emgloves of claim 1 by urethane and hard section, soft section and the heterogeneous system of nanophase forming with hydridization latex.
20. green latex glove according to claim 1 is to adopt the pickling process moulding process, mainly carries out gelling and film forming with ionic depositing method by the composite latex of described polyurethane aqueous dispersion of claim 18 and hydridization latex thereof.
21. the thickness of green latex glove according to claim 20 is 0.05～0.5mm, ideal thickness is 0.08～0.16mm, and the tensile strength of film is greater than 5MPa, and elongation is greater than 500%.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02110870 CN1439661A (en) | 2002-02-21 | 2002-02-21 | Preparation for multicomponent/multiphase environment protecting latex gloves |
| PCT/CN2002/000438 WO2003070811A1 (en) | 2002-02-21 | 2002-06-26 | Preparation of 'multicomponent/multiphase' green emulsoid gloves |
| AU2002318706A AU2002318706A1 (en) | 2002-02-21 | 2002-06-26 | Preparation of "multicomponent/multiphase" green emulsoid gloves |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02110870 CN1439661A (en) | 2002-02-21 | 2002-02-21 | Preparation for multicomponent/multiphase environment protecting latex gloves |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1439661A true CN1439661A (en) | 2003-09-03 |
Family
ID=27740083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02110870 Pending CN1439661A (en) | 2002-02-21 | 2002-02-21 | Preparation for multicomponent/multiphase environment protecting latex gloves |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1439661A (en) |
| AU (1) | AU2002318706A1 (en) |
| WO (1) | WO2003070811A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103096742A (en) * | 2010-06-22 | 2013-05-08 | 维健股份有限公司 | Polylactic acid gloves and methods of manufacturing same |
| US9145483B2 (en) | 2010-02-19 | 2015-09-29 | Smarthealth, Inc. | Polylactide hydrosol and articles made therefrom |
| CN107603202A (en) * | 2017-09-30 | 2018-01-19 | 南京晟强橡塑有限公司 | A kind of rubber pocket former polyurethane rubber bolster |
| CN107840997A (en) * | 2017-09-13 | 2018-03-27 | 杨磊 | The formula and preparation technology of a kind of polyurethane |
| CN111808260A (en) * | 2020-07-29 | 2020-10-23 | 四川尤博瑞新材料有限公司 | Thermosensitive condom based on waterborne polyurethane and preparation method thereof |
| CN111910440A (en) * | 2020-08-06 | 2020-11-10 | 安丹达工业技术(上海)有限公司 | Formula for cracking foam coating and fabric with cracking foam coating |
| CN112778480A (en) * | 2021-01-28 | 2021-05-11 | 南京优迪新材料科技有限公司 | Solvent-free polyurethane dispersion with good compatibility with butyronitrile latex and emulsion for glove coating |
| CN113370548A (en) * | 2021-02-01 | 2021-09-10 | 桂林恒保健康防护有限公司 | Polyurethane condom forming method based on wet process |
| CN114181371A (en) * | 2022-01-20 | 2022-03-15 | 星宇医疗科技股份有限公司 | Oil-resistant composite latex and preparation method thereof, disposable oil-resistant gloves and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100631792B1 (en) * | 2004-07-19 | 2006-10-09 | 호성케멕스 주식회사 | Method for producing antistatic polyurethane gloves using aqueous polyurethane emulsion composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1144813A (en) * | 1995-09-05 | 1997-03-12 | 韦特科公司 | Hypoallergenic coating composition for latex rubber gloves |
| NO20001902L (en) * | 1999-04-14 | 2000-10-16 | Dow Chemical Co | Polyurethane films and dispersions for their preparation |
| NO20001903L (en) * | 1999-04-14 | 2000-10-16 | Dow Chemical Co | Polyurethane films made from polyurethane dispersions |
-
2002
- 2002-02-21 CN CN 02110870 patent/CN1439661A/en active Pending
- 2002-06-26 WO PCT/CN2002/000438 patent/WO2003070811A1/en not_active Application Discontinuation
- 2002-06-26 AU AU2002318706A patent/AU2002318706A1/en not_active Abandoned
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9145483B2 (en) | 2010-02-19 | 2015-09-29 | Smarthealth, Inc. | Polylactide hydrosol and articles made therefrom |
| CN103096742A (en) * | 2010-06-22 | 2013-05-08 | 维健股份有限公司 | Polylactic acid gloves and methods of manufacturing same |
| CN108102321A (en) * | 2010-06-22 | 2018-06-01 | 维健股份有限公司 | Polylactic acid gloves and its manufacturing method |
| CN107840997A (en) * | 2017-09-13 | 2018-03-27 | 杨磊 | The formula and preparation technology of a kind of polyurethane |
| WO2019051857A1 (en) * | 2017-09-13 | 2019-03-21 | 杨磊 | Formulation and preparation process of modified polyurethane |
| CN107603202A (en) * | 2017-09-30 | 2018-01-19 | 南京晟强橡塑有限公司 | A kind of rubber pocket former polyurethane rubber bolster |
| CN111808260A (en) * | 2020-07-29 | 2020-10-23 | 四川尤博瑞新材料有限公司 | Thermosensitive condom based on waterborne polyurethane and preparation method thereof |
| CN111808260B (en) * | 2020-07-29 | 2021-05-25 | 四川尤博瑞新材料有限公司 | Thermosensitive condom based on waterborne polyurethane and preparation method thereof |
| CN111910440A (en) * | 2020-08-06 | 2020-11-10 | 安丹达工业技术(上海)有限公司 | Formula for cracking foam coating and fabric with cracking foam coating |
| CN112778480A (en) * | 2021-01-28 | 2021-05-11 | 南京优迪新材料科技有限公司 | Solvent-free polyurethane dispersion with good compatibility with butyronitrile latex and emulsion for glove coating |
| CN112778480B (en) * | 2021-01-28 | 2022-07-26 | 南京优迪新材料科技有限公司 | Solvent-free polyurethane dispersion with good compatibility with butyronitrile latex and emulsion for glove coating |
| CN113370548A (en) * | 2021-02-01 | 2021-09-10 | 桂林恒保健康防护有限公司 | Polyurethane condom forming method based on wet process |
| CN114181371A (en) * | 2022-01-20 | 2022-03-15 | 星宇医疗科技股份有限公司 | Oil-resistant composite latex and preparation method thereof, disposable oil-resistant gloves and preparation method thereof |
| CN114181371B (en) * | 2022-01-20 | 2023-11-21 | 星宇医疗科技股份有限公司 | Oil-resistant composite latex and preparation method thereof, and disposable oil-resistant glove and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2002318706A1 (en) | 2003-09-09 |
| WO2003070811A1 (en) | 2003-08-28 |
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