CN1891739A - Dip moldings, composition for dip molding and method for producing dip moldings - Google Patents
Dip moldings, composition for dip molding and method for producing dip moldings Download PDFInfo
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Abstract
从经由共轭双烯单体与烯键不饱和酸单体共聚制备的共轭双烯系橡胶胶乳成形的蘸塑成形品，其特征在于它是用一种水溶性多价金属盐交联的，而且实质上没有含硫硫化剂、该硫化剂用促进剂和氧化锌中任何一种；蘸塑成形用组合物；和蘸塑成形品制造方法。该蘸塑成形品几乎没有针孔，显示出良好手感，而且有令人满意的强度。Dip molded article formed from conjugated diene rubber latex prepared by copolymerization of conjugated diene monomer and ethylenically unsaturated acid monomer, characterized in that it is crosslinked with a water-soluble polyvalent metal salt , and substantially free from any of the sulfur-containing vulcanizing agent, the accelerator for the vulcanizing agent, and zinc oxide; the dip-molding composition; and the manufacturing method of the dip-molding molded article. The dip-molded article had almost no pinholes, exhibited a good hand, and had satisfactory strength.
Description
The application is to be that October 29 calendar year 2001, application number are dividing an application of 01821494.0 application for a patent for invention the applying date.
Technical field
The present invention relates to dip in and mould molding, dip in and be moulded shape with composition with dip in and mould the molding manufacture method, more particularly, relate to that pin hole is considerably less, feel is good and gratifying the dipping in of intensity moulded molding, the dipping in of starting raw material that is suitable as this molding is moulded the high-level efficiency manufacture method that shape is used composition and this molding.
Background technology
Usually, rubber gloves is widely used in housework work, various industry for example foodstuffs industry and electron device production and medical treatment (especially surgery).The requirement rubber gloves does not have pin hole, thereby feel well is convenient to work and on period does not break.
As rubber gloves, use is dipped in from natural rubber latex and is moulded those that obtain usually.Yet, because the trace amount of protein that exists in the rubber constituent, exist natural rubber latex gloves and may in some users, cause possibility hypersensitive, therefore, the someone proposed not exist the above possibility, with the synthetic rubber latex gloves made of acrylonitrile butadiene copolymer latex for example.
U.S. Patent No. 2,880,189 disclose a kind of dipping in is moulded shape and uses composition, said composition comprise a kind of water-insoluble polyvalent metal oxides and a kind of with one with the specific carboxy-modified acrylonitrile butadiene copolymer latex of ammonia neutral.Although be moulded shape and mould molding with dipping in of obtaining of composition and cause that possibility hypersensitive is very little from a kind of like this dipping in, because a lot of pin holes are arranged, thereby be necessary to dispose the defectiveness product of considerable number with the examination method.And then, from this not dipping in of sulfur-bearing be moulded shape and mould molding with dipping in of obtaining of composition and tend to low tensile stress (feel is good) is arranged when 300% elongation, but tensile strength bad (on period has the disruptive possibility).
WO 97/48765 discloses and has dipped in the gloves that are moulded shape with a kind of carboxy-modified acrylonitrile butadiene copolymer latex, eucasin, sulphur and vulcanization accelerator and without zinc oxide.A kind of dipping in of even now moulded molding has lower tensile stress and excellence when 300% extends tensile strength, but a lot of pin holes are arranged.
Mould during molding produces dipping in, to be moulded dipping in of forming on the shape model surface and to be moulded the sulfuration of shape layer in order to make dipping in, this dips in and is moulded the shape layer and meets with a vulcanisation step usually, and wherein, it was 100 ℃～130 ℃ heat-treated about 30 minutes～about 1 hour.A kind of like this thermal treatment needs a large amount of heat energy, thereby people expect the production method that a kind of efficiency is higher.
Summary of the invention
An object of the present invention is to provide dipping in that a kind of pin hole is considerably less, feel is good, intensity is enough and mould molding.Another object of the present invention provides dipping in of a kind of starting raw material that is suitable as above-mentioned molding and is moulded shape and uses composition.Another purpose again of the present invention provides the high productivity manufacture method of above-mentioned molding.
As artificial results of research with keen determination who realizes above-mentioned purpose and carry out such as present inventors, have been found that, the pH of the conjugate diene rubber latex of controlling a kind of conjugated dienes monomer and the copolymerization of a kind of ethylene linkage unsaturated acid monomer and obtaining, need not sulfur cross-linking and just can provide and a kind ofly demonstrate dipping in of satisfactory performance and mould molding, and on a kind of like this basis of discovery, finished the present invention.
That is, one aspect of the present invention provides following solution.
From a kind of conjugated dienes monomer and the copolymerization of a kind of ethylene linkage unsaturated acid monomer and the conjugate diene rubber latex dip moldings molded that obtains, wherein, this dips in, and to mould molding crosslinked with a kind of water-soluble polyvalent metal salt, and the carrying out that is shaped do not use sulfur-bearing vulcanizing agent, this vulcanizing agent with any in vulcanization accelerator and the zinc oxide in fact.
Another aspect of the present invention provides following solution.
Dip in and be moulded shape and use composition, said composition comprises a kind of conjugated dienes monomer and the copolymerization of a kind of ethylene linkage unsaturated acid monomer and the conjugate diene rubber latex that obtains, wherein, said composition has at least 8.5 pH, and do not contain the sulfur-bearing vulcanizing agent in fact, this vulcanizing agent is with any in vulcanization accelerator and the zinc oxide.
Another aspect again of the present invention provides following solution.
Dip in and mould the molding production method, comprise successively to dipping in to be moulded and adhere to a kind of step that comprises the latex coagulant of water-soluble polyvalent metal salt on the shape model, make this model be immersed in dipping in of a kind of conjugate diene rubber latex that comprises a kind of conjugated dienes monomer and the copolymerization of a kind of ethylene linkage unsaturated acid monomer and obtain and be moulded shape with in the composition and on this model surface, form one and dip in the step that is moulded the shape layer, said composition has at least 8.5 pH and does not contain the sulfur-bearing vulcanizing agent in fact, this vulcanizing agent vulcanization accelerator, with take off this after any in the zinc oxide and the drying and dip in the step that is moulded the shape layer.
Embodiment
Below explain in detail the present invention.
" conjugate diene rubber latex " means in the present invention and contains conjugated dienes monomer and ethylene linkage unsaturated acid monomer as the monomer mixture polymerization of basal component and a kind of conjugated dienes-ethylene linkage unsaturated acid copolymer rubber latex that obtains.This monomer mixture in these two kinds of monomer types, better contains this conjugated dienes monomer with the quantity bigger than this ethylene linkage unsaturated acid monomer.And then, this monomer mixture can also contain a kind of can with the additional ethylene linkage unsaturated monomer of above-mentioned two kinds of monomer type copolymerization.
The conjugate diene rubber latex that uses among the present invention better be comprise 30～90wt% conjugated dienes monomer, 0.1～20wt% ethylene linkage unsaturated acid monomer and 0～69.9wt% can be with the monomer mixture polymerization of the additional ethylene linkage unsaturated monomer of above monomer copolymerization and the copolymer emulsion that obtains.
This conjugated dienes monomer is not particularly limited, and the example comprises 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and chloroprene.These conjugated dienes monomers can use separately, and also can two or more types be used in combination and better used 1,3-butadiene or isoprene.
The monomeric usage quantity of conjugated dienes better is 30～90wt% of this monomer mixture, better 40～85wt%, 50～80wt% especially.When it was lower than 30wt%, resulting dipping in moulded molding hard feel arranged, and on the other hand, when it was higher than 90wt%, it is on the low side that these gloves do not keep its shape and tensile strength to tend to.
This ethylene linkage unsaturated acid monomer is not particularly limited, as long as it is a kind of for example ethylene linkage unsaturated monomer of carboxyl, sulfonic group or anhydride group of an acidic-group that has, the example comprises for example acrylic or methacrylic acid of ethylene linkage unsaturated monocarboxylic acid monomer; The unsaturated poly carboxylic acid monomer of ethylene linkage is methylene-succinic acid, toxilic acid or fumaric acid for example; The unsaturated multi-carboxy anhydride of ethylene linkage is maleic anhydride or citraconic anhydride for example; Ethylene linkage unsaturated sulfonic acid monomer is styrene sulfonic acid for example; With the unsaturated poly carboxylic acid part of ethylene linkage ester monomer for example fumaric acid one butyl ester, toxilic acid one butyl ester or toxilic acid one-2-hydroxy propyl ester.These ethylene linkage unsaturated acid monomers also can use with the form of alkali metal salts or ammonium salt.These ethylene linkage unsaturated acid monomers can use separately, also can two or more type combination use.In the middle of these ethylene linkage unsaturated acid monomers, be preferably and use the ethylene linkage unsaturated carboxylic acid, be more preferably and use the ethylene linkage unsaturated monocarboxylic, the good especially methacrylic acid that is to use.
The consumption of ethylene linkage unsaturated acid monomer better is 0.1～20wt% of this monomer mixture, better 1～15wt%, 2～6wt% especially.When it was lower than 0.1wt%, it is low that this dips in the tensile strength of moulding molding, and on the other hand, when it was higher than 20wt%, this dipped in the Boardy Feeling of moulding molding.
About can with the additional ethylene linkage unsaturated monomer of this conjugated dienes monomer and this ethylene linkage unsaturated acid monomer copolymerization, the example comprises ethylene linkage unsaturated nitrile monomer for example vinyl cyanide, methacrylonitrile, flumaronitrile, α-fluorine vinyl cyanide or α-cyanoethyl vinyl cyanide; Vinyl aromatic monomers is vinylbenzene, ring-alkylated styrenes or vinyl naphthalene for example; The fluoroalkyl Vinyl Ether is the fluoro ethyl Vinyl Ether for example; Ethylene linkage unsaturated acyl amine monomers is (methyl) acrylamide, N-methylol (methyl) acrylamide, N for example, N-dihydroxymethyl (methyl) acrylamide, N-methoxyl methyl (methyl) acrylamide, N-third oxygen methyl (methyl) acrylamide; Ethylene linkage esters of unsaturated carboxylic acids monomer is (methyl) methyl acrylate for example, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid tetrafluoro propyl ester, dibutyl maleinate, dibutyl fumarate, ethyl maleate, (methyl) vinylformic acid methoxy methyl esters, (methyl) vinylformic acid ethoxy ethyl ester, (methyl) vinylformic acid methoxy (ethoxy) ethyl ester, (methyl) vinylformic acid cyano group methyl esters, (methyl) 2 cyanoethyl acrylate, (methyl) vinylformic acid 1-cyano group propyl ester, (methyl) vinylformic acid 2-ethyl-own ester of 6-cyano group, (methyl) vinylformic acid 3-cyano group propyl ester, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) glycidyl acrylate, or (methyl) vinylformic acid dimethylin ethyl ester; With cross-linkable monomer for example Vinylstyrene, two (methyl) polyalkylene glycol acrylate ester, two (methyl) vinylformic acid polypropylene glycol ester, three (methyl) vinylformic acid, three (methylol) propane ester or (methyl) vinylformic acid pentaerythritol ester.These ethylene linkage unsaturated monomers can use separately, also can two or more type combination use.
In the middle of these monomers, be preferably and use ethylene linkage unsaturated nitrile monomer, vinyl cyanide especially.
The consumption of ethylene linkage unsaturated monomer better is 0～69.9wt% of this monomer mixture, better 0～59wt%, 14～48wt% especially.When it was higher than 69.9wt%, resulting dipping in moulded molding hard feel arranged.
Be used for producing the monomer mixture of this conjugate diene rubber latex good especially be to comprise 1,3-divinyl, vinyl cyanide and methacrylic acid, its composition better is respectively 40～79wt%, 20～45wt% and 1～15wt%, is better respectively 54～73wt%, 25～40wt% and 2～6wt%.
The conjugate diene rubber latex that uses among the present invention is normally produced with emulsion polymerisation process.Polymerization temperature during the letex polymerization is not particularly limited, but good especially be 45 ℃ or lower mould molding because this latex can stably be produced and can be obtained high and soft the dipping in of physical strength.Polymerization temperature during the letex polymerization is better in 10 ℃～45 ℃ scope.
In the production of this conjugate diene rubber latex, the addition means of this monomer mixture is not particularly limited, can adopt any method, for example, this monomer mixture adds all once that a part that method, this monomer mixture in the polymerization reactor supply to method in this polymerization reactor or this monomer mixture continuously adds in this polymerization reactor and this monomeric rest part supplies to the method in this polymerization reactor continuously.
The polymerization starter that uses in the production of this conjugate diene rubber latex is not particularly limited, but its particular instance comprises inorganic peroxy compounds for example Sodium Persulfate, Potassium Persulphate, ammonium persulphate, potassium superphosphate or hydrogen peroxide; The organic peroxy compound is hydroperoxidation diisopropylbenzene(DIPB), cumene hydroperoxide, t-butyl hydroperoxide, hydroperoxidation 1 for example, 1,3,3-tetramethyl butyl, 2,5-two hydroperoxidations-2,5-dimethylhexane, di-t-butyl peroxide, peroxidation two-α-cumyl, acetyl peroxide, peroxidation isobutyryl or benzoyl peroxide; With azo-compound for example Diisopropyl azodicarboxylate, azo two-2,4-methyl pentane nitrile or azo two methyl isobutyrates.These polymerization starters can use separately, also can two or more type combination use.Better use inorganic or organic peroxy compound because can stably produce latex and can obtain the physical strength height, molding is moulded in soft dipping in.The consumption of polymerization starter depends on its type to a certain extent, but is that benchmark better is 0.01～1.0 weight part with these monomer mixture 100 weight parts.
This inorganic or organic peroxy compound can be used in combination for example a kind of reductionoxidation polymerization initiator with a kind of reductive agent.This reductive agent is not particularly limited, and the example comprises and contains as-reduced metal ionic compound for example ferrous sulfate or cuprous naphthenate; Sulfoacid compound is methanesulfonic sodium for example; With amine compound for example xylidine or sodium ethylene diamine tetracetate.These reductive agents can use separately, also can two or more type combination use.The consumption of reductive agent depends on its type to a certain extent, but is that benchmark better is 0.03～10 weight part with this peralcohol 1 weight part.
In the middle of these initiators, be preferably and use the reductionoxidation polymerization initiator that has made up this peralcohol initiator and this reductive agent.
The emulsifying agent that uses in this conjugate diene rubber latex production is not particularly limited, but the example comprises nonionic emulsifier for example Voranol EP 2001, polyethenoxy alkylphenols, polyxyethylated ester or polyoxyethylene sorbitan alkyl ester; Anionic emulsifier, for example, lipid acid such as tetradecanoic acid, palmitinic acid, oleic acid or linolenic salt, the salt of alkyl benzene sulphonate (ABS) such as Sodium dodecylbenzene sulfonate, sulfuric acid high alcohol ester salt, or sulfo-succinic acid alkane ester salt; Cationic emulsifier, for example chlorination alkyltrimethylammonium, chlorination dialkyl ammonium or zephiran chloride ammonium; But with copolymerization emulsifying agent α for example, the sulfo group ester of beta-unsaturated carboxylic acid, α, the sulfuric ester of beta-unsaturated carboxylic acid or sulfo group alkyl aryl ether.Good especially anionic emulsifier or the nonionic emulsifier of being to use.These emulsifying agents can use separately, also can two or more type combination use.Be moulded the chemical stability of shape because emulsifying agent consumption influence is dipped in, thereby be that benchmark uses in 0.1～9wt% scope usually with this monomer mixture with latex.
In letex polymerization, can use polymerization auxiliary (reagent and additive in polymerization) in case of necessity, for example molecular weight regulator, granularity conditioning agent, oxidation inhibitor, sequestrant or oxygen scavenqer.
As the several mean particle sizes by measuring with the observation of transmission electron microscope, the granularity of this conjugate diene rubber latex better is 60～300nm, be more preferably 80～150nm.By for example adjusting the consumption of emulsifying agent and initiator, just can adjust to desirable numerical value to this granularity.
Of the present invention dipping in is moulded shape and comprises a kind of like this conjugate diene rubber latex with composition, and can by with its pH regulator at least 8.5, better 9.5～13, better 10.5～12 and make it not contain sulfur-bearing vulcanizing agent, this vulcanizing agent in fact with any obtaining in vulcanization accelerator and the zinc oxide.When dipping in when being moulded shape and being lower than 8.5, dip in the strength grade of moulding molding and descend, and will adjusting this pH, to make it be higher than 13 be very difficult with the pH of composition.
The sulfur-bearing vulcanizing agent of mentioning among the present invention is that a kind of high molecular weight chains of plasticity conjugate diene rubber that can make is cross-linked into a kind of cancellated material, and sulphur is exactly its representative.The sulfur-bearing vulcanizing agent roughly can be divided into inorganic sulfur-bearing vulcanizing agent and organic sulfur-containing vulcanizing agent; The former specific examples comprises sulphur (Powdered sulphur, flowers of sulfur, acidless sulfur, precipitated sulfur, colloid sulphur, polymerised sulphur, insoluble sulphur) and sulfur monochloride, the latter's particular instance comprises that those can be by thermal dissociation discharge active sulphur person, for example morpholine disulfide and curing alkylphenol.The specific examples of other organic sulfur-containing vulcanizing agent is listed in " go system industry brief guide " (rubber industry handbook) the 4th edition, the III chemical additive, and 1, vulcanizing agent, Japan rubber TIA compiles, and Japan rubber TIA publishes, in January, 1994.
Thereby the vulcanization accelerator of mentioning among the present invention be a kind of can be in the presence of the sulfur-bearing vulcanizing agent accelerated cure reaction demonstrate and shorten curing time, reduce curing temperature or reduce the material of the effect of sulfur-bearing vulcanizing agent.The specific examples of vulcanization accelerator comprises that thiazole is that for example 2-mercaptobenzothiazole zinc, thiocarbamide are that for example diphenyl thiourea, guanidine are that for example diphenylguanidine and aldehyde/ammonia and aldehyde/amine are for example vulkacit H of vulcanization accelerator to vulcanization accelerator to vulcanization accelerator to vulcanization accelerator.The concrete example of other vulcanization accelerator is listed in " go system industry brief guide " (rubber industry handbook) the 4th edition, the III chemical additive, and 3, vulcanization accelerator, Japan rubber TIA compiles, and Japan rubber TIA publishes, in January, 1994.
The existence of sulfur-bearing vulcanizing agent has increased dips in the number of moulding pin hole in the molding." not containing in fact " of this sulfur-bearing vulcanizing agent means that good especially is not contain, but it can be in the scope of not damaging the object of the invention, for example, 100 weight parts with the solid part of this conjugate diene rubber latex are benchmark, better 0.4 weight part, 0.2 weight part better at the most at the most also will be well less than 0.1 weight parts, good less than 0.05 weight part especially.
This vulcanizing agent has increased with the existence of vulcanization accelerator and has dipped in the number of moulding pin hole in the molding." not containing in fact " of this vulcanization accelerator means that good especially is not contain, but it can be in the scope of not damaging the object of the invention, for example, 100 weight parts with the solid part of this conjugate diene rubber latex are benchmark, better 0.4 weight part, 0.2 weight part better at the most at the most also will be well less than 0.1 weight parts.
The existence of zinc oxide has increased dips in the number of moulding pin hole in the molding." not containing in fact " of zinc oxide means that good especially is not contain, but it can be in the scope of not damaging the object of the invention, for example, 100 weight parts with the solid part of this conjugate diene rubber latex are benchmark, better at the most 0.7 weight part, better at the most 0.3 weight part, also to get well 0.1 weight part at the most.
" the carrying out of shaping do not used the sulfur-bearing vulcanizing agent in fact; this vulcanizing agent vulcanization accelerator; and any in the zinc oxide " or " not containing the sulfur-bearing vulcanizing agent in fact; this vulcanizing agent vulcanization accelerator; " with any in the zinc oxide mean that good especially is not use or do not contain the sulfur-bearing vulcanizing agent, this vulcanizing agent vulcanization accelerator, with any in the zinc oxide, but they can contain in the scope of not damaging the object of the invention, for example, 100 weight parts with the solid part of this conjugate diene rubber latex are benchmark, this sulfur-bearing vulcanizing agent is at most 0.4 weight part, this vulcanizing agent is at most 0.4 weight part with vulcanization accelerator, and this zinc oxide is at most 0.7 weight part; Be more preferably, this sulfur-bearing vulcanizing agent is at most 0.2 weight part, and this vulcanizing agent is at most 0.2 weight part with vulcanization accelerator, and this zinc oxide is at most 0.3 weight part.
Be moulded the pH of shape in order to adjust of the present invention dipping in, add a kind of alkaline matter with composition.The example of this alkaline matter comprises alkali-metal oxyhydroxide, for example lithium hydroxide, sodium hydroxide or potassium hydroxide; Alkali-metal carbonate, for example yellow soda ash or salt of wormwood; Alkali-metal supercarbonate, for example sodium bicarbonate; Ammonia; And organic amine compound, for example Trimethylamine 99 or trolamine.Good especially is alkali metal hydroxide and/or ammonia, is more preferably alkali metal hydroxide.For the formation of aggregate during preventing to add, these alkaline matters are usually with solution, better the form of the aqueous solution is added, and its concentration is 1～40wt%, 2～15wt% more preferably.
Dip in the method for shape that be moulded about adjusting this with the pH of composition, the example comprises the method for this conjugate diene rubber latex of prior adjustment, with in this conjugate diene rubber latex and the method for adjusting pH after desirable another kind of additive mixes, but this method is not particularly limited, if this dip in be moulded shape finally can be in desirable scope with the pH of composition.
This dips in and is moulded shape with the total solids level of composition normally 5～50wt%, better 10～45wt%, better 20～40wt%.When this content is too low, be difficult to obtain dipping in of desired thickness and mould molding, on the other hand, when it is too high, dips in and be moulded shape and use composition owing to its high viscosity is difficult to operate this, perhaps this dips in the thickness of moulding molding and tends to inhomogeneous.
Of the present invention dipping in is moulded shape and can contains standard additive in the scope of not damaging the object of the invention with composition, for example, and oxidation inhibitor, dispersion agent, tackifier, pigment, filler or tenderizer.Also can be used in combination another kind of latex for example natural rubber latex or synthetic polyisoprene latex, only otherwise damaging purpose of the present invention gets final product.
Be moulded shape with composition for of the present invention dipping in, not necessarily will meet with one and usually dip in and be moulded the aging step that shape will be carried out usually with composition.Just can not obtain dipping in of abundant intensity and mould molding owing to do not wear out, thereby to dip in the production of moulding molding be simple.
The water-soluble polyvalent metal salt that uses among the present invention is the salt of a kind of metal of the periodic table of chemical element the 2nd family, the 12nd family and the 13rd family, and the solubleness of at least 5 weight parts, better at least 20 weight parts is arranged in 25 ℃ 100 weight parts waters.Thereby having, this water-soluble polyvalent metal salt make the stable grade of the present latex particulate that is scattered in aqueous phase reduce the function that this present latex particulate is solidified.
The specific examples of water-soluble polyvalent metal salt comprises halogenide for example bariumchloride, calcium chloride, magnesium chloride, zinc chloride or aluminum chloride; Nitrate is nitrate of baryta, nitrocalcite or zinc nitrate for example; Acetate is barium acetate, lime acetate or zinc acetate for example; With vitriol for example calcium sulfate, sal epsom or Tai-Ace S 150.Specifically, calcium chloride and nitrocalcite are preferably.These water-soluble polyvalent metal salts better use with aqueous solution form.The concentration of this aqueous solution depends on the type of water-soluble polyvalent metal salt, but normally 5～70wt%, better be 20～50wt%.Normally 0 ℃～90 ℃ of temperature when this aqueous solution uses, better it is 30 ℃～70 ℃.
Of the present invention dipping in moulded molding and can be obtained by a kind of production method that comprises the following step successively: use a kind of dipping in to be moulded shape and to form one on the shape model surface and dip in the step that is moulded the shape layer and make the dried step that is moulded shape pull-up mould of dipping in dipping in to be moulded with composition and a kind of latex coagulant that comprises water-soluble polyvalent metal salt.
Dip in the formation step that is moulded the shape layer and can be divided into substantially that the anode peptizer dips in the method for moulding and Di Ke (Teague) peptizer dips in the method for moulding.Be preferably and form one with preceding a kind of method and dip in and be moulded the shape layer, because dipping in of obtaining like this moulded molding less uneven thickness is arranged.
The anode peptizer dips in the method for moulding and comprises successively: thus thereby one dipped in be moulded the shape model and be immersed in to make this latex coagulation liquid adhere to the step on this model surface in a kind of latex coagulation liquid that comprises water-soluble polyvalent metal salt and make this model be immersed in of the present invention dipping in and be moulded shape and dip in the step that is moulded the shape layer with on this model surface, forming one in the composition.Enlightening gram peptizer dips in the method for moulding and comprises successively: thus thereby one dipped in be moulded the shape model and be immersed in of the present invention dipping in and be moulded shape and dip in the step of the coating that is moulded shape usefulness composition and make this model be immersed in a kind of latex coagulation liquid that comprises water-soluble polyvalent metal salt on this model surface one of formation and dip in the step that is moulded the shape layer with on this model surface, forming this in the composition.Also can form big the dipping in of film thickness and be moulded the shape layer by repeating one of these two kinds of methods or alternately repeat these two kinds of methods.
When dipping in when being moulded shape, this dips in the model temperature that is moulded the shape model and this and dips in and be moulded shape with the temperature of composition normally room temperature～90 ℃, better 40 ℃～80 ℃.The anode peptizer dip in the method for moulding this dip in be moulded the shape model in this latex coagulation liquid buried time length and adhered to dipping in of this latex coagulation liquid be moulded the shape model this dip in be moulded shape with composition in buried time length can suitably adjust, make that can obtain dipping in of desired thickness is moulded the shape layer.
Dipping in of obtaining like this is moulded the shape layer and washes with water before the drying more fortunately.Washing with water here means this is dipped in and is moulded the shape layer and is immersed in the water that submergence is about 2～about 60 minutes in 40 ℃ more fortunately～70 ℃ the hot water, thereby removes water-soluble impurity (for example excessive emulsifying agent, water-soluble polyvalent metal salt etc.).This operation can be dipped at this and be carried out after being moulded shape layer drying, but carries out before drier, because can remove water-soluble impurity more expeditiously.Carrying out this operation can significantly improve this and dip in the tensile strength of moulding molding.
Dipping in of obtaining like this is moulded the shape layer high water content, need carry out drying.This drying is so carried out, so that this dips in the water-content that is moulded the shape layer and better becomes 5wt% or lower, better 2wt% or lower.About drying means, can adopt to relate to by means of the outer heating of ir radiation or hot blast or by means of the method for the internal heating of frequency electromagnetic waves.Drying by means of hot blast is good especially.Normally 60 ℃～95 ℃ of drying temperatures, better be 70 ℃～85 ℃, normally about 10～about 120 minutes of time of drying.
Because drying can be given this and be dipped in and be moulded the shape layer with abundant intensity, thereby this one deck is dipped in from this be moulded on the shape model demoulding and just can provide a kind of dipping in and mould molding.As release method, employing be it to be dipped in the method that is moulded the demoulding on the shape model from this with hand, perhaps make the method for its demoulding by means of water pressure or compressed air pressure.
Before the demoulding, it is met with in 100 ℃～150 ℃ temperature, 10～120 minutes thermal treatment, but of the present invention dipping in is moulded shape and only carry out above-mentioned drying with composition and just can provide dipping in of abundant intensity and mould molding.And then, if wish, after the demoulding, it is met with in 60 ℃～120 ℃ temperature, 10～120 minutes further thermal treatment.
Mould in the molding of the present invention dipping in, for the mole number of the acidic group of bonded ethylene linkage unsaturated acid in this conjugate diene rubber latex, the ratio of mole number that comes from the polyvalent metal of employed water-soluble polyvalent metal salt better is 0.2～1.5, be more preferably 0.3～1.3, good especially be 0.35～0.8.When this ratio was in this scope, this dips in moulded the tensile strength that molding has excellence.
This ratio is that thereby quantitatively to determine to come from the numerical value that the mole number of the polyvalent metal of included water-soluble polyvalent metal salt obtains definite divided by forming this mole number that dips in the acidic group of bonded ethylene linkage unsaturated acid in the conjugate diene rubber latex of moulding molding by this being dipped in mould molding to make this burning part change into metal chloride at high temperature incineration and with hydrochloric acid.When quantitatively determining the mole number of this polyvalent metal, be not to come from this polyvalent metal salt but can be defined as the contamination that the composition of identical polyvalent metal causes quantitatively if exist a kind of, then its quantity will be revised before this calculating.
Quantity by bonded ethylene linkage unsaturated acid in this conjugate diene rubber latex of suitable adjustment, this dips in and is moulded shape with the concentration of the pH of composition, this water-soluble polyvalent metal salt and/or dip in the condition of moulding etc., just can adjust to desirable numerical value to this ratio.
Of the present invention dip in mould tensile stress that molding can easily reach for 300% when elongation for less than 4.5MPa, better less than 3.5MPa, better less than 3.0MPa, excellent feel and tensile strength are 20MPa at least, better 25MPa, 30MPa better at least at least.
Here tensile stress of mentioning and tensile strength mean those that measure with method described in the embodiment.
Of the present invention dipping in moulded molding and can be produced to such an extent that make it to have the thickness of about 0.1～about 3mm, and can be especially suitably as the thin product use of thickness with about 0.1～about 0.3mm.Specifically, it is suitable as curable product for example baby bottles nipple, dropper, pipe or thermos flask; Toy or sporting equipment be balloon, doll or ball for example; Industrial products are pressure forming bag or bladder tank for example; Surgical glove, domestic purpose gloves, agricultural gloves, fishing gloves and industrial gloves; And fingerstall.It is particularly suitable as thin surgical glove.
Followingly explain the present invention in more detail with reference to embodiment." part " among the embodiment and " % " all by weight, unless otherwise prescribed.
Performance estimating method
pH
With pH meter (M12:HORIBA corporate system) 25 ℃ of mensuration.The latex of measuring has 45% solids content, and the dipping in of mensuration is moulded shape has 30% solids content with composition.
The tensile stress and the tensile strength of 300% elongation
According to ASTM D 412, dip in the punching press of Die-c dumbbell and to be moulded the shape rubber gloves, make a kind of test piece.With the draw speed of a Tensilon universal testing machine (RTC-1225A, KK Orientech makes), this test piece is carried out the tensile stress and the fracture tensile strength of 300% elongation and measured with 500mm/min.
The tensile stress in 300% when elongation is more little, and it is just good more that this dips in the feel of moulding molding.
The rubber gloves transparency
Dip in the transparency that is moulded the shape rubber gloves with the visual method assessment.
The pin hole number
A rubber gloves is filled water, and after 30 minutes, the point that the water of the inside is just being spilt on this outer surface of glove is defined as a pin hole, number needle outlet number.100 rubber glovess of each specimen preparation, and measure the sum of the pin hole that forms in all rubber glovess.
The quantity of bonded methacrylic acid in the conjugate diene rubber latex
The part that rear copolymer latex is finished in the collection copolyreaction is removed residual unreacted monomer as sample, condenses according to JIS K 6392 then and drying, obtains a kind of solid rubber.
Accurately take by weighing the about 0.2g of this solid rubber sample, be dissolved among the pyridine 100ml, the solution that obtains like this carries out the neutralization titration of carboxyl in this multipolymer with 0.2N potassium hydroxide alcoholic solution under nitrogen atmosphere as indicator with thymolphthalein.The needed potassium hydroxide quantity of carboxyl from this solid rubber that neutralizes is determined the quantity (in wt%) of bonded methacrylic acid in this solid rubber.
Dip in and mould polyvalent metal in the molding/in conjunction with the methacrylic acid mol ratio
Mould molding 0.5g, place a metallic crucible, in electric furnace, handle and made its burning in 2 hours thereby accurately take by weighing to dip in 600 ℃.Then, remaining ash content as working curve, is measured polyvalent metal chloride concentration that in this solution dissolved come from this water-soluble polyvalent metal salt with capillary electrophoresis with calcium chloride water with the dissolving of 10g 0.1N aqueous hydrochloric acid in this metallic crucible.
The condition determination of this capillary electrophoresis is as follows:
Metering equipment: CAPI-3200 capillary electrophoresis system (big electronics corporation system)
Buffer reagent: 2mM imidazoles
5mM 2-hydroxy-iso-butyric acid
100 μ l acetate/100ml distilled water
Wavelength: 215nm
Institute's making alive: 25kV
Measuring method: indirect method
Obtain the mole number (R) of this polyvalent metal with following formula (1):
In the formula, C is the muriatic concentration of dissolved polyvalent metal (wt% is in calcium chloride) in the 10g 0.1N hydrochloric acid
Mcacl
2Be molecular weight=111 of calcium chloride.
Under the situation that this conjugate diene rubber latex uses separately, used herein dipping in moulded the mole number in conjunction with methacrylic acid (M) that contains in the molding and obtained with following formula (2):
Be moulded under the situation that shape contains the composition beyond this conjugate diene rubber latex in composition dipping in, this dips in and moulds the quantity of rubber constituent in the molding is according to the quantity correction of supplementary component.
This dips in moulds polyvalent metal in the molding/in conjunction with the methacrylic acid mol ratio by the R value is obtained divided by the M value.
Production Example 1～6
A withstand voltage polymerization reactor washes away with nitrogen, add 100 parts of the totals of monomer shown in the table 1, as 0.5 part of uncle's dodecyl mercaptans of molecular weight regulator, 132 parts of soft water, as 1.5 parts of the Sodium dodecylbenzene sulfonatees of emulsifying agent, as 0.3 part of the Potassium Persulphate of polymerization starter with as 0.05 part of the sodium ethylene diamine tetracetate of reductive agent, the temperature of reaction that is reflected at 37 ℃ was carried out 30 hours, and the Sodium dimethyldithiocarbamate 40min that adds then as reaction terminating agent stops this polymerization for 0.1 part.In all cases, polymerisation conversion all is at least 97%.
After the unreacted monomer in removing the latex that obtains like this, adjust the pH of this copolymer emulsion, provide solids content and be 45%, pH is conjugate diene rubber latex A～F of 8.0 with 28% ammoniacal liquor.
Table 1
| Production Example | ||||||
| 1 | 2 | 3 | 4 | 5 | 6 | |
| Monomer is formed (part) vinyl cyanide 1,3-butadiene methacrylic acid | 37 58 5 | 37 59.5 3.5 | 37 61.5 1.5 | 20 72 8 | 28 68 4 | 37 63 - |
| The conjugate diene rubber latex | A | B | C | D | E | F |
| Quantity (wt%) in conjunction with methacrylic acid | 5.2 | 3.4 | 1.4 | 8.3 | 4.2 | 0 |
Embodiment 1
With 5% potassium hydroxide aqueous solution the pH of conjugate diene rubber latex A is adjusted to 10.0 and solids content adjusted to 30%, prepared a kind of dipping in and be moulded shape and use composition.
One is moulded the shape glove model dipping in of 60 ℃ of heating, at a kind of 20 parts in nitrocalcite, nonionic emulsifier (Emulgen-810 that passes through to mix as water-soluble polyvalent metal salt, KAO. Corp. SA's system) 0.05 part and 80 parts in water and dipped in for 10 seconds in the latex coagulant aqueous solution that obtains, put forward then, 60 ℃ of dryings 10 minutes, thereby this water-soluble polyvalent metal salt is adhered on this model surface.
Then, this glove model that has been coated with this peptizer is moulded shape with 15 seconds of submergence in the composition above-mentioned dipping in, puts forward then, dip in and be moulded the shape layer thereby on this glove model surface, form one.This thing is 20 ℃ of dryings 5 minutes, 80 ℃ further dry 20 minutes, on this glove model surface, provide a solid cladding.At last, this solid cladding is stripped down from this glove model, providing a kind of thickness is that 0.1～0.2mm (dip in and mould molding down together by) glove form.This assessment result of moulding molding of dipping in is listed in the table 2.
Embodiment 2
Repeat the program of embodiment 1, different is, this dips in and is moulded shape and adjusts to 11.0 with the pH of composition with 5% potassium hydroxide aqueous solution.The results are shown in Table 2.
Embodiment 3
Repeat the program of embodiment 2, different is after 80 ℃ of dryings 20 minutes, by 120 ℃ of further thermal treatments 20 minutes, to obtain a kind of dipping in and mould molding.The results are shown in Table 2.
Embodiment 4
Repeat the program of embodiment 2, different is, before 80 ℃ of dryings 20 minutes, will have this to dip in the glove model submergence 5 minutes in 50 ℃ distilled water that is moulded the shape layer, thereby remove water-soluble impurity.The results are shown in Table 2.
Embodiment 5 and 6
Repeat the program of embodiment 4, different is to use each replacement conjugate diene rubber latex A among conjugate diene rubber latex B listed in the table 1 and the C.The results are shown in Table 2.
Embodiment 7 and 8
Repeat the program of embodiment 4, different is to use each replacement conjugate diene rubber latex A among conjugate diene rubber latex D listed in the table 1 and the E.The results are shown in Table 2.
Embodiment 9
By 0.1 part in 0.1 part of mixed oxidization titanium in ball mill, 40% beta-naphthalenesulfonic-acid-0.05 part of formaldehyde condensation products sodium-salt aqueous solution and water, prepare a kind of titanium oxide liquid dispersion, as white pigment.Mix 0.25 part of this liquid dispersion and 250 parts of conjugate diene rubber latex E (corresponding to 100 parts of solids contents), adjust its pH to 11.0 with 5% potassium hydroxide aqueous solution then, and its solids content adjusted to 30%, provide a kind of dipping in and be moulded shape and use composition.
Repeat the program of embodiment 8, different are to use, and this dipping in is moulded shape and uses composition.The results are shown in Table 2.
Comparative example 1
By in ball mill, mixing 3.4 parts in 1 part on 2-mercaptobenzothiazole zinc, 1.5 parts in sulphur, 1 part in zinc oxide, 40% beta-naphthalenesulfonic-acid-0.5 part of formaldehyde condensation products sodium-salt aqueous solution and water, obtain a kind of vulcanizing agent dispersion.Mix 7.4 parts of this vulcanizing agent dispersions and 250 parts of conjugate diene rubber latex A (corresponding to 100 parts of solids contents), its pH adjusts to 10.0 with 5% potassium hydroxide aqueous solution then, its solids content is adjusted to 30%, the mixture ageing that obtains like this 1 day provides a kind of dipping in and is moulded shape and uses composition.Repeat the program of embodiment 3, different are to use, and this dipping in is moulded shape and uses composition.The results are shown in Table 2.
Comparative example 2
By in ball mill, mixing 2.5 parts in 1 part on 2-mercaptobenzothiazole zinc, 1.5 parts in sulphur, 40% beta-naphthalenesulfonic-acid-0.5 part of formaldehyde condensation products sodium-salt aqueous solution and water, obtain a kind of vulcanizing agent dispersion.Mix 5.4 parts of this vulcanizing agent dispersions and 250 parts of conjugate diene rubber latex A (corresponding to 100 parts of solids contents), its pH adjusts to 10.0 with 5% potassium hydroxide aqueous solution then, its solids content is adjusted to 30%, the mixture ageing that obtains like this 1 day provides a kind of dipping in and is moulded shape and uses composition.Repeat the program of embodiment 3, different are to use, and this dipping in is moulded shape and uses composition.The results are shown in Table 2.
Comparative example 3
By 0.5 part in 1 part on mixed oxidization zinc in ball mill, 40% beta-naphthalenesulfonic-acid-0.5 part of formaldehyde condensation products sodium-salt aqueous solution and water, obtain a kind of zinc oxide dispersion.Mix 2.0 parts of this dispersions and 250 parts of conjugate diene rubber latex A (corresponding to 100 parts of solids contents), its pH adjusts to 10.0 with 5% potassium hydroxide aqueous solution then, its solids content is adjusted to 30%, the mixture ageing that obtains like this 1 day provides a kind of dipping in and is moulded shape and uses composition.Repeat the program of embodiment 3, different are to use, and this dipping in is moulded shape and uses composition.The results are shown in Table 2.
Comparative example 4
Repeat the program of embodiment 1, different is, uses the pH of a kind of wherein this conjugate diene rubber latex A to keep 8.0 constant and solids content is adjusted to 30% dip in and be moulded shape and use composition.The results are shown in Table 2.Dip in when this glove form and to mould molding when this glove model is peeled off, this dips in moulds molding and draws thin or break, and can't obtain dipping in of gratifying glove form and mould molding.
Comparative example 5
Repeat the program of embodiment 2, different is to use conjugate diene rubber latex F to replace conjugate diene rubber latex A.The results are shown in Table 2.Dip in when this glove form and to mould molding when this glove model is peeled off, this dips in moulds molding and draws thin or break, and can't obtain dipping in of gratifying glove form and mould molding.
Table 2
| Embodiment | Comparative example | |||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 1 | 2 | 3 | 4 | 5 | |
| Dip in and be moulded shape usefulness composition conjugate diene rubber latex sulphur, (part) vulcanization accelerator, (part zinc oxide, (part) titanium dioxide, the pH of (part) composition | A - - - - 10.0 | A - - - - 11.0 | A - - - - 11.0 | A - - - - 11.0 | B - - - - 11.0 | C - - - - 11.0 | D - - - - 11.0 | E - - - - 11.0 | E - - - 0.1 11.0 | A 1.5 1.0 1.0 - 10.0 | A 1.5 1.0 0 - 10.0 | A - - 1.0 - 10.0 | A - - - - 8.0 | F - - - - 11.0 |
| Washing heat-treat condition drying is (80 ℃ before dry, 20mim) heating (120 ℃, 20min) | Be not- | Be not- | Be not | Be- | Be- | Be- | Be- | Be- | Be- | Be not | Be not | Be not | Be not- | Be not- |
| Polyvalent metal/in conjunction with methacrylic acid (mol ratio) | 0.40 | 0.46 | 0.47 | 0.46 | 0.71 | 1.28 | 0.39 | 0.59 | 0.58 | 0.53 | 0.44 | 0.50 | 0.11 | - |
| Dip in the transparency of stress (MPa) tensile strength (MPa) rubber gloves when being moulded 300% elongation of shape resistance *Pin hole number (hole) | 2.5 24.5 transparent 3 | 2.8 27.3 transparent 2 | 2.9 27.5 transparent 2 | 3.4 45.6 transparent 1 | 2.8 39.8 transparent 1 | 2.3 28.4 transparent 0 | 4.4 43.5 transparent 1 | 2.3 35.2 transparent 0 | 2.4 35.8 muddy opaque 7 | 6.2 28.4 muddy opaque 38 | 3.5 24.3 muddinesses 20 | 5.2 23.7 muddy opaque 28 | 0.9 4.5 transparent- | 1.3 3.5 transparent- |
From found that the following fact shown in the table 2.
Be moulded shape and mould molding with dipping in of obtaining of composition comparison good hand feeling and good tensile are arranged from comprising dipping in of sulphur, vulcanization accelerator and zinc oxide, but pin hole number very big (comparative example 1).
Not containing zinc oxide and moulding molding by dipping in of adding that sulfur vulcanization obtains has good hand feeling, but tensile strength is low and pin hole number big (comparative example 2).
Also do not contain dipping in of vulcanization accelerator and be moulded shape and mould molding with dipping in of obtaining of composition the comparison good hand feeling is arranged from promptly not containing sulphur, but tensile strength is low and pin hole number quite big (comparative example 3).
Never contain sulphur, vulcanization accelerator or zinc oxide and its pH and be lower than dipping in of the scope stipulated among the present invention and be moulded shape and mould molding with dipping in of obtaining of composition excellent feel is arranged, but tensile strength is very low and be not suitable as to dip in and mould molding (comparative example 4).
Moulding molding from dipping in of obtaining of the conjugate diene rubber latex that does not wherein have copolymerization ethylene linkage unsaturated acid monomer has excellent feel, but tensile strength is very low, and is not suitable as to dip in and moulds molding (comparative example 5).
Compare with these comparative examples, dipping in of stipulating from the present invention is moulded shape and moulds molding with dipping in of obtaining of composition excellent feel, the excellent very little pin hole of tensile strength, number are arranged.It is transparent that the dipping in of embodiment 1～8 moulded molding, if but be ready that chromatic molding can be easily produced in expection.
When comparing embodiment 2 and 3, find not vulcanize necessary thermal treatment and just can obtain dipping in of abundant tensile strength and mould molding.
Dry preceding water Xian provides excellent feel and the dipping in of tensile strength of outstanding improvement moulded molding (embodiment 4～9).
Industrial applicability
Of the present invention dipping in moulded formed products considerably less pin hole, good feel and sufficient intensity arranged. Also can easily obtain transparent dipping in and mould formed products. Of the present invention dipping in is moulded shape and is suitable as this with composition and dips in and mould formed products manufacturing initiation material, and manufacture method of the present invention can high production rate ground be made this and dipped in and mould formed products.
Claims (4)
1. from a kind of conjugated dienes monomer and the copolymerization of a kind of ethylene linkage unsaturated acid monomer and the conjugate diene rubber latex dip moldings molded that obtains, wherein, this dips in, and to mould molding crosslinked with a kind of water-soluble polyvalent metal salt;
This conjugate diene rubber latex is to obtain by the copolymerization with the additional ethylene linkage unsaturated monomer of these monomer copolymerizations of this conjugated dienes monomer of 30～90wt%, this ethylene linkage unsaturated acid monomer of 0.1～20wt% and 0～69.9wt% energy;
Solid part 100 weight parts with this conjugate diene rubber latex are benchmark, and the sulfur-bearing vulcanizing agent is that the vulcanization accelerator of 0.4 weight part, this vulcanizing agent at the most is 0.4 weight part at the most, and zinc oxide is 0.7 weight part at the most; With
This dips in moulds tensile stress and 20MPa or the higher tensile strength that is lower than 4.5MPa when molding has 300% elongation.
2. mould molding according to dipping in of claim 1, wherein, solid part 100 weight parts with this conjugate diene rubber latex are benchmark, and the vulcanization accelerator that this sulfur-bearing vulcanizing agent is 0.2 weight part, this vulcanizing agent at the most is 0.2 weight part at the most, and this zinc oxide is 0.3 weight part at the most.
3. mould molding according to dipping in of claim 1, wherein, the carrying out of this shaping do not used in the vulcanization accelerator of sulfur-bearing vulcanizing agent, this vulcanizing agent and the zinc oxide any.
4. mould molding according to dipping in of claim 1, wherein, for the mole number of the acidic group of bonded ethylene linkage unsaturated acid in this conjugate diene rubber latex, the ratio of mole number that comes from the polyvalent metal of employed water-soluble polyvalent metal salt is 0.2～1.5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP330936/2000 | 2000-10-30 | ||
| JP2000330936 | 2000-10-30 | ||
| JP053748/2001 | 2001-02-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018214940A Division CN1292017C (en) | 2000-10-30 | 2001-10-29 | Dip-molded article, composition for dip-molding, and method for manufacturing dip-molded article |
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| CN1891739A true CN1891739A (en) | 2007-01-10 |
| CN100439427C CN100439427C (en) | 2008-12-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8975351B2 (en) | 2008-09-26 | 2015-03-10 | Lg Chem, Ltd. | Latex resin composition for rubber gloves without sulfur and vulcanization acceleator and method of manufacturing dip-formed article using the composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4102844A (en) * | 1973-09-22 | 1978-07-25 | Bayer Aktiengesellschaft | Dipped articles of rubber |
| US5084514A (en) * | 1990-11-14 | 1992-01-28 | Reichhold Chemicals, Inc. | Latex gloves with improved donnability |
| US5369166A (en) * | 1991-09-30 | 1994-11-29 | Nippon Zeon Co., Ltd. | Copolymer latex, method for preparing the same and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8975351B2 (en) | 2008-09-26 | 2015-03-10 | Lg Chem, Ltd. | Latex resin composition for rubber gloves without sulfur and vulcanization acceleator and method of manufacturing dip-formed article using the composition |
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