CN1125749A - Coating composition, method of using it and article coated with same - Google Patents

Abstract

The present invention relates to an aqueous composition which comprises a natural rubber modified with a graft-polymerised methylmethacrylate polymer such as a graft-polymerised methylmethacrylate an acrylic polymer, such as a poly(acrylonitrile/ butadiene/carboxylate) latex, an acrylonitrile synthetic rubber and optionally other ingredients. The other ingredients may be a quaternary ammonium surfactant and a polysiloxane. The composition is applied to an article such as of natural and/or synthetic rubber to effect coating. The process is especially suited to coating of gloves intended for industrial, medical or domestic applications.

Description

Coating composition, its using method and coated article thereof

The present invention relates to coating composition, also relate to said composition and be used for the method for goods and the goods that apply with said composition.Although said composition is not special-purpose, for example is specially adapted to by natural or gloves that synthetic rubber is made and is used for as the multiple use under medical treatment, food, industry or the home environment.

In the past in 10 years or age more early, seen that in the various industry of requirement to(for) the protection of hand is all improving, as hospitality industry, chemical industry, engineering circle and family expenses.For example, when current legal requirements may contact with the noxious chemical as its part work as the staff, their employer just needed its worker is provided the protection of hand.Protective layer of skin must be arranged with the cross infection between the patient that prevents them and they self the professional of medical courses in general and dentistry occupation, thereby the demand of disposable natural rubber medical gloves is increased greatly.

Because the demand of these gloves is increasing, so their service requirements becomes stricter.Goods in all medical sale of the U.S. all must meet the US-FDA standard.Use different rules in other country.In addition, the other requirement that also exists or must or wish, this depends on predetermined purposes, now it is summarized as follows:

For medical, many users require shallow (white/colourless) color;

Necessary and the skin-compatible of gloves, promptly anallergic;

Gloves must have necessary physical properties, as tensile strength, tear strength, extension at break, modulus and not such as defectives such as the impurity of hole, embedding, stain, irregular thicknesses;

Gloves do not contain particulate matter, so that do not play the particle of dirt in use or do not have lubricant powder to stay on the surface of having handled; This point is especially important for electronic unit uses, but also is high request in curable product;

Gloves should be with such raw material manufacturing, and this raw material has chemical resistant properties to the environment that will contact such as oil, lubricating grease, fatty deposits etc., and this point is even more important to industrial gloves;

Product should have the aging property of enough storage periods;

When gloves were made with natural rubber latex or the adulterant that contains this latex, the floating preteins content of these gloves should be zero or very low.

Above-mentioned two aspects need further to handle: skin-friendliness and chemical resistant properties.Medical gloves mainly is based on the gloves of being made by natural rubber polymkeric substance (cis 1,4 polyisoprene), and normally gratifying.Yet people know that they are insufficient and in some cases with regard to its chemical resistant properties, also have the unacceptable reaction of sensitization skin, and its reason is that the natural rubber latex Ruzhong innately exists some by protein derived antigen.With regard to the consistency of skin, but when the proteic polymkeric substance of seldom extracted amount is made gloves obvious benefit is being arranged by not containing albumen or only containing, therefore can be as under the situation of some natural rubber gloves, not producing anaphylaxis.

As for the back on the one hand, known gloves based on natural rubber are insufficient to the patience that non-polar solvent such as hexane, decane, oil, kerosene, toluene etc. are had, wherein contact and can cause rubber diaphragm rapidly and significant the expansion with solvent, loss of physical properties, and often cause and ruin through cracks.Report has been arranged, and long-term operation technique might cause the gloves film to absorb fat and the result causes that intensity reduces.These situations all are common knowledge and when condition is in harsh state, for example in chemical operation, just are necessary to use based on polymkeric substance as poly-(acrylonitrile-butadiene), or the gloves of poly-(chloroprene).Although comparing with natural rubber, these polymkeric substance have different stress/strain characteristics, for example poly-(acrylonitrile-butadiene) gloves are harder or have a higher modulus of stretch of inherent, but their molecular composition guarantees that the patience to above-mentioned solvent is superior than those gloves of being made by natural rubber, is preferred therefore.This gloves of past are mainly used in industry and are thick (for example 0.5-2mm), and are shaped on cotton lining sometimes.Now, thin a kind of being used on some medical treatment and the industrial use that does not have the fiber lining.

The present invention can satisfy above-mentioned one or more requirement condition with regard to its various embodiments or embodiment.Its purpose is to provide the high-grade coating composition and uses its application glove, especially coating rubber gloves.Gloves itself are by synthetic or natural rubber, or made by the adulterant of synthetic and natural rubber, but owing to mention already, synthetic rubber is preferred sometimes.Gloves of the present invention are high-grade with regard to its processing and/or surfacing.

The gloves of manufacturing of the present invention can be suitable for any special purposes or application, and are for example aforesaid any.Yet a kind of preferred purposes is a medical gloves.The term " medical gloves " that is used for this paper is defined as usually at the known various types of gloves of medically protecting hand of industry, as " test gloves ", " operate and use gloves ", " surgeon uses gloves: " after death using gloves ", " dental care gloves " or the like.Preferably, these gloves be all by natural rubber or wherein the natural rubber adulterant that accounts for main (＞50%) polymkeric substance make.When being used for this paper, term " rubber " means any natural or synthetic rubber or the adulterant of natural rubber and polymkeric substance, unless opposite specified otherwise is arranged.

The gloves that need must be further considered specially.Good white be easy to produce but chlorination and when aging (g.v.) loss of either large or small degree is arranged.

Normally just necessary in advance with the consistency of human skin, especially under the situation that gloves have on for a long time in the medical care precess process of continuity, sometimes this character is called " hypoallergenic ".This character is normally by selecting the non-irritating chemical in prescription, and guarantees to give suitable washing produce by handling the deleterious chemical that produces to remove in making processes.Yet, have been found that for some healthcare givers, even the gloves of describing also may cause stimulation even dermatitis when reusing like this.In order to overcome back one problem, be desirable to provide a kind of protective layer so that rubber and skin are separated.Such protective layer must be harmless and not influence skin.

The aging of storage period also is an important factor.All can degrade when all rubber products are aging, but prepare, process and store under appropriate condition when this product, then degradation process is slowly.Yet, a kind of gloves is proposed in specification sheets of the present invention, it relatively is preferred with common product, because this gloves have stronger performance reservation when aging.

The ordinary method of making medical gloves is to handle the rubber surface of inherent viscosity with biocompatibility pulvis such as starch.Need not this material, gloves just are difficult for putting on or taking off, and the operation of finger is subjected to strictly limiting.Yet the existence of pulvis means that when using, some pulvis are left probably or stay on one's body the patient on the glove surface.

Use two kinds of different processing schemes at present.First kind of requirement is with in rare two surfaces of chlorine water solution-treated gloves one or two.Doing like this can be from chemically improving rubber surface, thereby has the surface of low frictional resistance, easy handling and use.Although this is simple method, this processing is deleterious to the physical properties of gloves, and especially the sterilization after, it make film colour-darkening and also the damage storage period aging property.

Second kind of scheme comprises with such method handles gloves, and this method is that different polymeric membrane is coated on the rubber surface to produce the performance of dressing, taking off and operating of being easy to of necessity.The case description of this method in following patent specification, i.e. US-A-4499154, US-A-5132129, EP-A-0413467, EP-A-0198514 and EP-A-0455323.

The polymkeric substance that is suitable for this outer blooming must be easy to apply and have suitable character, and promptly it should be a flexible, with rubber surface adhesion, can operate satisfactorily and nonirritating.

Studies show that to allergic having higher (500ppm or more) free or extractible proteic medical rubber glove can cause sensitization patient's anaphylactic shock recently.Although these people only represent the very people of small proportion, the floating preteins content that makes gloves is low as much as possible clearly to be rational.An object of the present invention is to provide a kind of medical gloves, wherein press the floating preteins content that standard detecting method is measured, low as far as possible when based on natural rubber, when being used for the synthetic gloves, then be zero maybe.

For the gloves of being made by polymer latex (or natural or synthetic), basic manufacturing technology is well-known, for example described in US-A-5014362 or the US-A-5084514.

Make gloves with batch process or chain type (chain) method, in this method, earlier model is immersed in the setting accelerator solution, calcium salt normally, drying is put into latex compounds then, then drying, crimping (beading), washing or lixiviate, sulfuration and the demoulding.After this, carry out some finishing operations, inspection and packing.The gloves of making in this way have natural surface tackiness, and it hinders and dress, takes off and general operation.This surface tackiness usually with lubricator powder such as talcum powder overcome, perhaps under the medical gloves situation, use biological absorbable W-Gum, this starch can apply in the online or off-line method of production process.In some cases, with rare chlorine water solution-treated gloves, this solution can react to improve its smoothness with rubber surface.Yet this method is relatively more expensive, complicated operation, and might make product reduction storage period or the aging property that fade low.

Especially relevant medical gloves has two general manufacture method.These two kinds of methods depend on forming model are suitably immersed setting accelerator, immerse then in the rubber latex compound, then are dry, washing (leaching) and drying/sulfuration and the final step of the demoulding.The additional offline method also can be implemented, for example extra drying, efflorescence, chlorination etc.The difference of two kinds of methods only is to finish on the mode of dipping.A kind of method needs dipping in batches, wherein before entering next step a collection of model is immersed in the operation.Another is to use chain type line dipping, wherein will continuously immerse attached to the model of continuous chain in the bath of various setting accelerator and latex.Can make by the either party's method in these currently known methodss by the gloves that the present invention makes.Implement on line or under off-line.

The internal surface of gloves or outside surface or two coating compositions that the surface all can have system of the present invention, this system combination can obtain fabulous, about put on and remove, the character of the handiness of good operability and finger, have surface, obtainable protein content with the bonding non-irritating polymer layer of rubber very low or zero, good light color and than conventional products better storage period of aging property.

If necessary, this novel method also can combine with existing last repair method, as chlorination, so that a side of gloves can be handled and another side is a chlorating with polymeric membrane.Certainly, also might make the one side efflorescence and the another side polymer treatment.

Be used for polymeric system of the present invention and be the adulterant of water base polymkeric substance, it can not expect to have necessary character, yet is surprisingly found out that after enlarging development work, can realize this target.

Therefore, first aspect of the present invention provides a kind of aqueous coating composition, and it contains natural rubber, acrylate copolymer, vinyl cyanide synthetic rubber and optional a spot of batching of the methacrylate type polymer modification of useful graft polymerization.

Preferably, the methyl methacrylate polymer that is used for the graft polymerization of modified natural rubber is the polymethylmethacrylate of graft polymerization or the polyethyl methacrylate of graft polymerization.

Preferably, the amount of the graftomer of the methacrylate type of modified natural rubber is 0.1%-10%, better is 0.5%-4.0%, and that good especially is 1.0%-2.0%.Graftomer content is preferably 35%-60%, though can variable, nominal is about 40%.

Preferably, the amount of acrylate copolymer is 0.1%-10%, is more preferably 0.5%-8.0% (for example 0.5%-6.0%), and that good especially is 1.0%-4.0%.This polymkeric substance can be the acrylic polymer latex that is generally used for making the emulsion paint type.This acrylate polymer emulsion all is suitable in very wide scope, and it is based on the monomer blend of monomer such as vinylacetate, methyl acrylate or acrylate and vinylbenzene, ethene, methacrylic ester, vinylchlorid etc.

Preferably, the elastomeric amount of vinyl cyanide is 0.1%-5%, is more preferably 0.5%-3.0%, and that good especially is 1.0%-2.0%.

Acrylonitrile polymer is a kind of polymkeric substance that is formed by the acrylonitrile monemer unit at least, yet preferably also mixes other monomer such as divinyl and/or carboxylic acid monomer.Good especially acrylonitrile polymer is that with similar basic gloves polymer phase ratio, this polymkeric substance contains for example vinyl cyanide of 30%-40% by the preparation of vinyl cyanide, divinyl and carboxylic acid monomer's terpolymer.

Preferably, the amount of polysiloxane is 0.05%-10%, 1.0%-5.0% more preferably, and that good especially is 1.0%-3.0%.A kind of best polysiloxane is the polydimethylsiloxane that molecular weight mixes in the 12000-15000 scope, as emulsion.

Preferably, the amount of quaternary ammonium surfactant is 0.05%-5%, is more preferably 0.1%-2.0%, and that good especially is 0.5%-1.5%.Preferred quaternary ammonium surfactant comprises cetyl trimethylammonium bromide, or the chloride salt of cetyl trimethyl or its mixture.

Though be not absolutely necessary for purposes of the invention, if but find sometimes in above-mentioned specified polymeric system, to add a kind of lubricant 0.1%-3.0%, the aqueous dispersion such as the stearate of Zinic stearas or calcium stearate of preferred 0.5%-2.0% then can make to handle to reach excellent.When the gloves of finished product are considered to " no powder ", expression is suspected with this point that powder adds; Yet, can think that in drying/rotation technological process excessive pulvis removes and the thing that stays can be dissolved in the rubber from glove surface the dry heat process, cause rubber surface not have pulvis by the standard method measurement.

The per-cent of listing is above all represented by the total solids level of the polymerization system of common mensuration.Specify the per-cent that all per-cents that this paper enumerates all are by weight unless have on the contrary.

Gloves natural and/or that synthetic rubber is made can apply by several diverse ways.Now briefly be illustrated.

First method is applicable to that natural rubber gloves also is applicable to the rubber gloves of being made by available polychloroprene latex on the market or poly-(acrylonitrile/butadiene/carboxyl) latex.Gloves are to adopt the collimation method at intermittence of being furnished with the wet type demoulding (high-pressure water jet) to make in the usual way.The gloves of the self-wetted demoulding are in the future packed in the gloves rotary drum, and this rotary drum is similar to the industrial washing that prior art is known, and rotates 10-20 minute, as 10 minutes to 15 minutes to discharge excessive water.After excessive water is discharged from, add the aqueous polymerization system.Gloves were rotated 10-20 minute once more, discharge excessive mixture again.Then gloves are transferred in the rotary drum drier, the usefulness warm air descended dry 30-60 minute at 60 ℃-80 ℃.Get gloves ready and send to check and packing.

The gloves that second method is suitable for natural rubber gloves and is made by poly-(acrylonitrile/butadiene/carboxylicesters) or polychloroprene latex.They all are by the preparation of the chain type collimation method of standard.In order to help the demoulding, in this method, in setting accelerator and in the bath of rearmounted drying machine slurry, add some pulvis usually.It is standard reagent that biology can absorb starch.But pulvis is a lime carbonate in the method.Press then and carry out special disposal.

Pack into back in the rotary drum of gloves is added 0.5% acetate, and begins to rotate and all be neutralized and wash off up to all pulvis, usually about 10 minutes just enough.Discharge the acid back and add polymerization system; Carry out and the identical program of top first example.In both cases, the polymerization system on the gloves two sides is identical.

It should be noted that in above-mentioned three kinds of methods, the polymerization system on two faces of gloves is identical.In sense of touch, the aspect such as put on and have under the particular requirement situation, the present invention can apply different polymerization systems with each face of gloves.This is to illustrate in the third method, and this method also shows how to exempt extra off-line procedure when needs.This method also is suitable for natural and synthetic two kinds of rubber glovess.In other words, it also can at random exempt the necessity to extra off-line step, and is suitable for the method for intermittent type line and chain type line.Here, the normal setting accelerator aqueous mixture with calcium salt and nitrate increases because of polymerization system.In this case, the nonionogenic tenside that must add 2.0%-4.0% in polymerization system to be keeping colloidal stability in the setting accelerator, and preferably uses the organopolysiloxane of minimum concentration and aqueous emulsion of dimethyl polysiloxane fluid or it is all saved.This improvement of setting accelerator need be adjusted by carrying out common in the prior art on a small quantity to dipping and drying machine parameter.This method is further improved so that can on-line operation.Off-line procedure that need not be extra with the slurry bath of aqueous polymerization system replacement pulvis so that when the demoulding, can make the product two sides contain polymeric coatings.

In this method, gloves are dipped in setting accelerator and the latex with normal way and behind main drying machine, are dipped in the polymerization system drying, demoulding drying again.So, bathe and slurry, might change coating system so that the two sides has different last processing by improving setting accelerator.

As mentioned above, might make hybrid-type coating system, causing a face is polymer treatment and another side is a chlorating.This point illustrates in the method for the 4th kind of gloves that are applicable to natural rubber gloves or made by poly-(acrylonitrile/butadiene/carboxylicesters) latex.The gloves of making on intermittent type or chain type line are dipped in the aqueous polymerization mixture with conventional setting accelerator, and this setting accelerator contains some lime carbonate dust pulvis, replace slurry to bathe drying, the demoulding again but use aqueous polymerization to bathe.Make their chlorinations with usual method then and turn up.The chlorination layer in the inside of gloves and the polymerization object plane outside.Such system does not have all advantages of two sides polymeric coatings with regard to good color and best unaged and aging tensile property.

The 5th kind of method also is suitable for by gloves natural and/or that synthetic latex is made.It also is a combination treatment and similar with the 4th kind of method.Improve the chain type line online chlorination can be provided and combine with using polymeric coagulants by the third method is described behind main loft drier.This method has been got rid of the needs to off-line operation, and therefore the product that obtains can detect and pack at any time.

At length the present invention will be described in the description by following non-limiting examples now.

Embodiment 1

Natural rubber gloves (40kg the is heavy) capacity of putting into that takes out on the intermittent type line from wet type demoulding section is 800 liters a rotary drum, rotates 10 minutes to remove superfluous water, adds following polyblend then.

Polymethylmethacrylate with 40% graftomer connects

Branch polymkeric substance natural rubber latex, 50.0% total solids level ... ..32.0kg

Acrylic polymer latex, 48% total solids level ... ... ..16.7kg

The carboxylated latex of Polybutadiene Acrylonitrile, 52% is always solid

Body burden ... ... ... ... ... ... ..15.4kg

Aqueous emulsion of dimethyl polysiloxane fluid, total solids level 36%.........66.7kg

Cetyl trimethylammonium bromide, total solids level 10%........8.0kg

Water, remollescent or deionized ... ... ... ... 661.2kg

All compositions are all pressed solid weight meter.Before adding the gloves rotary drum, prepare mixture.

Gloves rotate with mixture and discharged polymeric system in 20 minutes again.It can further handle gloves once more with slight topping up.Gloves rotate 10 minutes again to remove superfluous liquid, in the rotatory drier under 60 ℃ dry 30-60 minute again.Every gloves weight increases 0.5%-3.0% (by weight).Relatively listing in table 1 and the table 2 of the gloves character that gloves character of making in this way and ordinary method are made by the latex of same type.Can clearly be seen that the advantage of coating material system.The gloves that polymer-coated is crossed are put on easily and are sloughed, and can mesh well when using and very flexible.The gloves that applied polymkeric substance use the method for B.S.5736 part 6,8 that skin irritation and susceptibility are tested, and the result is satisfactory.

Embodiment 2

Take out with the intermittent type line from the wet type ejection phase and be 800 liters the rotary drum by gathering gloves (40kg) capacity of putting into that (acrylonitrile/butadiene/carboxylicesters) latex makes, rotate 10 minutes, add following polyblend again to remove excessive water:

Polymethylmethacrylate with 40% graftomer connects

Branch polymkeric substance natural rubber latex, 50% total solids level ... ..32.0kg

Acrylic polymer latex, 48% total solids level ... ... 16.7kg

Poly-(acrylonitrile/butadiene/carboxylicesters) latex, 52% is total

Solids content ... ... ... ... ... ... .14.4kg

Aqueous emulsion of dimethyl polysiloxane fluid, total solids level 36%..........66.7kg

Cetyl trimethylammonium bromide, total solids level 10%.........8.0kg

Deionized water ... ... ... ... ... ... 661.2kg

All the components is solid by weight.Said mixture mixes before being added to rotary drum.Gloves rotate with this mixture and discharged polymeric system in 20 minutes again.The polymeric system of discharging is used for processing subsequently with slight topping up.Gloves were rotated 10 minutes so that remove excessive polymkeric substance again, and forward 70-80 ℃ rotatory drier inner drying 30-60 minute to.Every gloves weight increases to the 0.5%-3.0% of original weight.Physicals is listed in table 3.The gloves that polymer-coated is crossed are easy to put on and remove, and have good handiness and engagement when using.Polymer layer is adhered to rubber surface, and can not come off under with the gloves normal running.The gloves that scribble polymeric system are to skin irritation and susceptibility, detect according to the method for B.S.5736 part 6 and 8, and the result is satisfactory.Detected result according to the physical properties of these example gloves is listed in the table 3 hereinafter.

Embodiment 3

This example has two change schemes, and one is used natural rubber gloves and another uses the gloves of being made by poly-(acrylonitrile/butadiene/carboxylicesters) latex.In all cases, be to take from wet type demoulding section and the capacity of putting into is 800 liters a rotary drum from the gloves of intermittent type line (40kg is heavy), rotate the excessive water of discharge after 10 minutes, add following polyblend again:

Polymethylmethacrylate with 40% graftomer connects

Branch polymkeric substance natural rubber latex, 50.0% total solids level ... 16.0kg

Acrylic polymer latex, 48% total solids level ... ... 33.3kg

The carboxylated latex of Polybutadiene Acrylonitrile, 52% is always solid

Body burden ... ... ... ... ... ... 15.4kg

Aqueous emulsion of dimethyl polysiloxane fluid, total solids level 36%..........44.4kg

Cetyl trimethylammonium bromide, total solids level 10%.........8.0kg

Water, remollescent or deionized ... ... ... ... .682.9kg

All the components is solid by weight.Mixture is to prepare before being added to the gloves rotary drum.

Gloves rotate with mixture and discharge polymeric system after 20 minutes.Its available slight topping up and can be used for further processing once more.Gloves rotated 10 minutes again discharging fifth wheel, 60 ℃ rotatory drier inner dryings 30-60 minute.Every gloves weight increases 0.5%-3.0% (weight).Relatively listing in table 1 and the table 2 of the finished product gloves that the character of the natural rubber gloves of making in this way and ordinary method are made with identical latex.The physical properties of synthetic latex gloves and example 2 are described similar.

The advantage of coating material system is clearly visible.The gloves that were coated with polymkeric substance are easy to put on and remove, and have good engagement and handiness when using.

Embodiment 4

Natural rubber hand (40kg the is heavy) capacity of putting into that takes out from the intermittent type line from wet type demoulding section is 800 liters a rotary drum, rotates 10 minutes to discharge superfluous water, adds following polyblend then:

Polymethylmethacrylate with 40% graftomer connects

Branch polymkeric substance natural rubber latex, 50.0% total solids level ... 32.0kg

Acrylic polymer latex, 48% total solids level ... ... 66.7kg

The carboxylated latex of Polybutadiene Acrylonitrile, 52% is always solid

Body burden ... ... ... ... ... ... .7.7kg

Aqueous emulsion of dimethyl polysiloxane fluid, total solids level 36%..........44.4kg

Cetyl trimethylammonium bromide, total solids level 10%........80.0kg

The water dispersion of Zinic stearas, total solids level 35%..........45.7kg

Water, remollescent or deionized ... ... ... ... .523.5kg

All the components all is by solid weight meter.Mixture is to prepare before being added to the gloves rotary drum.

Gloves rotated 20 minutes with mixture and discharge polymeric system; It can further handle gloves once more with slight topping up.Gloves were rotated 10 minutes again so that remove excessive thing, then 60 ℃ rotatory drier inner drying 30-60 minute.Every gloves weight increases 0.5%-3.0% (weight).Gloves character of making by this method and ordinary method are relatively listed in table 1 and the table 2 by the gloves character of latex production of the same race.The advantage of coating material system is clearly visible.The gloves that were coated with polymkeric substance are easy to put on and remove, and have fabulous handiness when using.

Embodiment 5

This example also has two kinds of change schemes, and each uses natural rubber and synthetic rubber gloves.In all cases, gloves be with ordinary method in the setting accelerator that 5% lime carbonate is arranged preparation on the chain type line and before the demoulding behind main drying machine the outside surface of application glove in the slurry of 9% lime carbonate.Pack into the gloves (40kg) of the dry demoulding in the wet type rotary drum and add 400 liters 0.5% acetate.Gloves were stirred 10 minutes.Discharge acid, washed gloves again with water 5 minutes.Add following mixture after the drainage water:

Polymethylmethacrylate with 40% graftomer connects

Branch polymkeric substance natural rubber latex, 50.0% total solids level ... ..24.0kg

Acrylic polymer latex, 48% total solids level ... ... ..58.3kg

The carboxylated latex of Polybutadiene Acrylonitrile, 52% is always solid

Body burden ... ... ... ... ... ... ..30.8kg

Aqueous emulsion of dimethyl polysiloxane fluid, total solids level 36%............44.4kg

Cetyl trimethylammonium bromide, total solids level 10%..........40.0kg

The aqueous dispersion of Zinic stearas, total solids level 35%...........2.3kg

Water, remollescent or deionized ... ... ... ... 600.2kg

Gloves were rotated 15 minutes in above-mentioned polyblend, discharged then 10 minutes, following dry 60 minutes in 60 ℃ again.

Natural rubber gloves has these characteristics:

Outward appearance ... ... ... ... ... ... .... good

Color ... ... ... ... ... ... .... white

Polymer coating ... ... ... ... ... ... the .. adhesion

Sensation, flexible ... ... ... ... ... .... good

Wearability ... ... ... ... ... ... ... .. is good

The property removed ... ... ... ... ... ... ... good

Engagement ... ... ... ... ... ... .... good

Physical properties ... ... ... ... ... ... ... good

(as table 1 and 2)

It is aging ... ... ... ... ... ... .... good

Aging, sterilized ... ... ... ... ... .... good

The synthetic rubber gloves have and the similar character of embodiment 2 gloves.

Embodiment 6

This law is a kind of natural rubber gloves that adopts intermittent type or the preparation of chain type line method, make its two sides all have polymerization to remove the method for layer, described in above-mentioned embodiment 4, improving setting accelerator makes it contain polymkeric substance, this polymkeric substance can form the coated inside of gloves when dipping, but skin tends to turn up when the demoulding when using.Prepare following setting accelerator and supply with 800 liters of setting accelerator grooves:

Polymethylmethacrylate with 40% graftomer connects

Branch polymkeric substance natural rubber latex, 50.0% total solids level ... ..32.0kg

Acrylic polymer latex, 48% total solids level ... ... ..66.7kg

The carboxylated latex of Polybutadiene Acrylonitrile, 52% is always solid

Body burden ... ... ... ... ... ... ..15.4kg

Nonionogenic tenside is as 12 or more carbon atoms

Long-chain alcohol and at least 12 ethylene oxide molecule polymeric polyoxies

The ethene condenses, total solids level 10%..................16.8kg

Cetyl trimethylammonium bromide, total solids level 10%..........8.0kg

Water, remollescent or deionized ... ... ... ... ..261.1kg

The preparation said mixture also mixes with following mixture:

Nitric hydrate calcium ... ... ... ... ... ... 80.0kg

Water ... ... ... ... ... ... ... .320.0kg

Carry out the intermittent type of standard or chain type line pickling process except for being easy to the demoulding when method finishes, have been found that the last stage, before the drying before the setting accelerator dipping, should immerse in 1.0% the potassium oleate at the model cleaning course.Model is immersed in the following mixture:

Polymethylmethacrylate with 40% graftomer connects

Branch polymkeric substance natural rubber latex, 50.0% total solids level ... ..32.0kg

Acrylic polymer latex, 48% total solids level ... ... ..66.7kg

The carboxylated latex of Polybutadiene Acrylonitrile, 52% is always solid

Body burden ... ... ... ... ... ... ..15.4kg

Aqueous emulsion of dimethyl polysiloxane fluid, total solids level 36%............44.4kg

Cetyl trimethylammonium bromide, total solids level 10%..........80.0kg

The aqueous dispersion of Zinic stearas, total solids level 35%...........2.3kg

Water, remollescent or deionized ... ... ... ... 559.2kg

Make gloves drying, the demoulding, check and packing.The character of this gloves is similar to the above-mentioned gloves that obtain.

Embodiment 7

The description of this example is a kind of adopts intermittent type or the preparation of chain type collimation method to have the method that there are polymer coated synthetic rubber gloves on the two sides, this method does not have additional offline to handle, in this processing, to apply the setting accelerator of model surface by modification, make undercoat as mentioned above, adopt polymerization bath on the line simultaneously to apply outside surface (air surface).

Prepare following setting accelerator for 800 liters setting accelerator groove:

Polymethylmethacrylate with 40% graftomer connects

Branch polymkeric substance natural rubber latex, 50.0% total solids level ... ..32.0kg

Acrylic polymer latex, 48% total solids level ... ... ..66.7kg

Poly-(acrylonitrile/butadiene/carboxylicesters) latex, 52% is total

Solids content ... ... ... ... ... ... 15.4kg

Nonionogenic tenside, former as 12 or 12 above carbon

Sub-long-chain alcohol with have 12 at least, best 30 condensed epoxies

The polyethylene oxide condensation compound of the molecule of ethane, total solids contains

Amount 10%......................................16.8kg

Cetyl trimethylammonium bromide, total solids level 10%...........8.0kg

Deionized water ... ... ... ... ... ... ..181.1kg

Order by statement prepares said mixture, mixes with following mixture again:

Nitric hydrate calcium ... ... ... ... ... ... 120.0kg

Deionized water ... ... ... ... ... ... ..360.0kg

The production method of carrying out standard is except in order to be easy to the demoulding when method finishes, finding will to clean before dry model, to be dipped in 2% the potassium oleate aqueous solution be favourable.Behind main drying machine, the gloves on the model are immersed the same polymer slurry that is used for embodiment 6 gloves dipping.Gloves have the character similar to embodiment 2.

Embodiment 1,3 and 4 natural rubber gloves and tabulation down 1 are compared further with the conventional gloves described in 2 and are detected.The accordingly result of synthetic latex gloves is listed in the table 3.

Table 1

Unaged the wearing out of character gloves of the natural rubber gloves of routine and coated polymer, 14 days/70 ° were worn out, 22h/100 ° of type T.S. E.B. M 300% T.S. E.B. M 300% T.S. E.B. M 300%

(MPa) (%) (MPa) (MPa) (%) (MPa) (MPa) (%) (MPa) P, 32.1 865 1.52 31.9 1,011 1.31 34.2 956 1.28non-s (99%) (107%) P, 33.2 882 1.61 26.3 969 1.11 24.4 987 1.14s (79%) (74%) C, 31.0 855 1.69 6.2 857 0.86 8.4 957 0.88non-s (20%) (27%) C, 30.6 873 1.71 000 4.2 831 0.76s (14%) P1,33.2 888 1.63 29.8 917 1.68 29.0 915 1.68non-s (90%) (87%) P1,32.8 885 1.58 29.5 866 1.56 30.8 963 1.44s (90%) (94%) P2,33.7 885 1.58 31.8 942 1.50 33.1 905 1.62non-s (94%) (98%) P2,30.4 935 1.32 28.1 785 1.66 28.6 951 1.46s (92%) (94%) P3,34.7 883 1.62 31.5 988 1.56 33.2 862 1.60non-s (91%) (96%) P3,30.3 947 1.31 30.0 833 1.59 31.5 931 1.53s (99%) (104%) abbreviation keyword: T.S.=tensile strength E.B.=extension at break, M 300%=300% modulus is carried out tensile testing according to B.S.903 part A 2; The P.=powder; Non-s=did not sterilize; The s=irradiation sterilization is crossed; The C.=chlorating; P1=example 1 coated polymer; P2=example 2 coated polymers; P3=example 3 coated polymers.

Table 2

Pulvis and extractible protein content glove type pulvis content, the extractible albumen of mg/ gloves, 2.8 20 examples, 1 0.5 17 examples, 2 0.2 6 examples 3 3.1 5 of 218.0 166 chlorinations of ppm powder

The pulvis Determination on content is with normes Francaises method NFS90-000.

The mensuration of protein content is with the improved Lowry method of Rubber Research Institute of Malays-ia; Referring to J.Nat.Rubb.Res.7 (3), 206-218 (1992).

Table 3

By flooding by poly-(acrylonitrile/butadiene/carboxylicesters) glue

The unaged tensile strength of the physical properties of the gloves of the difference processing that breast is made and the polymkeric substance/chlorination of the conventional efflorescence polymer-coated of effect test, Mpa 27.4 30.6 28.5 extension at breaks, % 660 643 620 modulus, 300%, Mpa 3.13 4.20 4.04 aging 22h/100 tensile strength, Mpa 27.4 27.9 27.9 extension at breaks, % 604 633 630 modulus, 300%, Mpa 4.43 3.40 3.77 pulvis content, the good good paint adhesion of the good good easiness of removing of the easiness-powdery no pulvis of good good hand of the poor-medium good wearing of ppm 107.1 3.0 2.2 engagements do not have the medium good residual bad nothing of back pulvis of using of pulvis handiness and do not have

The tensile testing program is according to ISO37-1977 (E).

Pulvis content, the US-FDA-ASRM method of inspection.

According to specification sheets of the present invention, the change scheme of described example and other example is pressed in the scope of the present invention of appended claims qualification.These schemes will become clearer concerning the those skilled in the art of affiliated technical field.

Claims (36)

1, a kind of aqueous coating composition, it contains natural rubber, acrylate copolymer, vinyl cyanide synthetic rubber and optional a small amount of Synergist S-421 95 of the methacrylate type polymer modification of useful graft polymerization.

2, a kind of composition by claim 1, it also contains the optional a small amount of batching with polysiloxane and quaternary ammonium surfactant form.

3, a kind of composition by claim 2, wherein polysiloxane is that molecular-weight average is 12,000-20,000 polydimethylsiloxane.

4, a kind of composition by claim 2 or 3, wherein the amount of polysiloxane is counted 0.05%-10.% by the weight of total solids level.

5, a kind of by each composition among the claim 2-4, wherein quaternary ammonium surfactant is selected from cetyl trimethylammonium bromide and palmityl trimethyl ammonium chloride and composition thereof.

6, a kind of claim 2 or 5 composition, wherein the amount of quaternary ammonium surfactant is counted 0.05%-5% by the weight of total solids level.

7, a kind of composition by aforementioned each claim is wherein counted 0.1%-10% with the amount of the natural rubber of graft polymerization methacrylic ester polymer modification by the weight of total solids level.

8, a kind of composition by aforementioned each claim, wherein the methacrylate type polymkeric substance of graft polymerization is the methyl methacrylate of graft polymerization.

9, a kind of composition by aforementioned any claim, wherein the amount of the graftomer in the natural rubber of the methyl methacrylate polymer modification of using graft polymerization is 35%-45% by weight.

10, a kind of composition by aforementioned each claim, wherein the amount of acrylate copolymer is counted 0.1%-10% by the weight of total solids level.

11, a kind of composition by aforementioned each claim, wherein acrylate copolymer is the acrylate copolymer synthetic latex.

12, a kind of composition by aforementioned each claim, wherein the elastomeric amount of vinyl cyanide is counted 0.1%-5% by the weight of total solids level.

13, a kind of composition by aforementioned each claim, wherein the vinyl cyanide synthetic rubber is the carboxylated polymkeric substance of Polybutadiene Acrylonitrile.

14, a kind of composition by claim 13, wherein poly-(acrylonitrile/butadiene/carboxylicesters) polymkeric substance exists with the latex form.

15, a kind of composition by aforementioned each claim also contains a kind of lubricant.

16, a kind of composition by claim 14, wherein the amount of lubricant is counted 0.1%-3% by the weight of total solids level.

17, a kind of composition by claim 15 or 16, wherein lubricant is a Zinic stearas.

18, a kind of aqueous coating composition is basically as described above described in any one embodiment.

19, a kind of method of coated article, this method comprise apply toward described goods a kind of by each aqueous coating composition among the claim 1-18.

20, a kind of method by claim 18, this method are included in after the demoulding goods with the demoulding of described compositions-treated wet type, drying then.

21, a kind of method by claim 19 or 20, wherein the lime carbonate pulvis is used to effectively carry out the dry type demoulding.

22, a kind of by each method among the claim 19-21, wherein said composition uses by flooding these goods in described goods heating back.

23, a kind of by each method among the claim 19-22, wherein goods are to be made by the material that contains natural rubber.

24, a kind of by each method among the claim 19-22, wherein goods are made by containing elastomeric material.

25, a kind of method by claim 24, wherein synthetic rubber comprises poly-(acrylonitrile/butadiene/carboxylicesters) polychloroprene polymers.

26, a kind of by each method among the claim 23-25, wherein said goods are gloves.

27, a kind of method by claim 26, wherein setting accelerator is used for the manufacturing processed of described gloves, and makes by each composition among the claim 1-15 and mix with setting accelerator.

28, a kind of by claim 26 or 27 method, wherein said composition be painted on the face of gloves and another face of gloves through chloridized.

29, a kind of by claim 26 or 27 method, wherein said composition is painted on the face of gloves and another side carries out pulvis and handles.

30, described in the arbitrary as described above basically embodiment of a kind of method of application glove, this method.

31, a kind of usefulness is by the goods of each composition coating among the claim 1-18.

32, a kind of goods by claim 31, these goods are to be made by the material that contains natural rubber.

33, a kind of goods by claim 31, these goods are made by containing elastomeric material.

34, a kind of goods by claim 33, wherein synthetic rubber comprises poly-(acrylonitrile/butadiene/carboxylicesters) polymkeric substance.

35, a kind of by each goods among the claim 32-34, these goods are gloves.

36, a kind of coated glove is basically as described in relevant any one embodiment in front.