CN105722908A - Polymeric compositions comprising polyisoprene - Google Patents
Polymeric compositions comprising polyisoprene Download PDFInfo
- Publication number
- CN105722908A CN105722908A CN201480059749.1A CN201480059749A CN105722908A CN 105722908 A CN105722908 A CN 105722908A CN 201480059749 A CN201480059749 A CN 201480059749A CN 105722908 A CN105722908 A CN 105722908A
- Authority
- CN
- China
- Prior art keywords
- composition
- latex
- polymer
- coating
- elastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/0055—Plastic or rubber gloves
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/015—Protective gloves
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/04—Appliances for making gloves; Measuring devices for glove-making
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/02—Copolymers with acrylonitrile
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Gloves (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
Polymeric, elastomeric, or latex compositions including a water-based emulsion of a polyisoprene polymer; a first accelerator comprising at least one of a thiourea, a thiazo!e, or a dialkyl dithiocarbamate, or combinations thereof; a second accelerator comprising a thiuram or a xanthogen, or a combination thereof; at least one antioxidant; at feast one vulcanizing agent; and an activator; wherein a total amount of the first accelerator and the second accelerator ranges from 0.2 to 2.5 PHR of the polymeric, elastomeric, or latex composition and the polymeric, elastomeric, or latex composition is free of diphenyl guanidine or casein, are disclosed.
Description
Background of invention
Invention field
Embodiment of the present invention relate generally to polymer composition and goods prepared therefrom, more specifically it relates to the elastomeric article with the physical property of improvement and the method manufacturing this based article.
Description of related art
Latex formulations, elastomer formulation or polymer formulations are used to prepare the pliability product with barrier property.This based article (such as elastomeric article) includes condom and glove.Glove are used to many industries if building, industry and medical treatment and family are to protect the both hands of user.These type of glove many comprise synthetic latex or Heveatex or thermoplastic elastomer (TPE), such as nitrile rubber, polychlorobutadiene or polyurethanes.
For medical applications, for instance examination gloves and surgical glove, glove promote protection antibacterial, virus and microorganism.Especially for surgical glove, in the operation process using dissecting knife, tweezers, shears, mosquito forceps etc. glove for such as can by pulling force cause tear, to have resistance be important for abrasion etc..But, the glove prepared by synthetic polyisoprenes are relatively more weak than the glove (that is, the glove in rubber tree or guayule source) prepared by natural rubber latex, using and particularly are being prone to break in life-time service process, adding doctor's infection risk to patient, vice versa.Therefore, medical personnel must put on double gloves, namely puts on two glove in order to perform the operation on hand at each, and this causes the loss of tactility and adds operating expense.Medical worker can be made owing to needing to overcome the stiffness of two both hands sets and tired and make flexibility ratio reduce additionally, dress two both hands sets.
It addition, thin and flexible elastomeric article is more comfortable for a user.But, the thinness of the elastomeric article of such as glove and condom and pliability are with tear resistance for cost.
Trial major part for strengthening the physical property of the polyisoprene for elastomeric article all have failed.Such as, various accelerator have been used for rubber formulation with improve resistance to wear and tear resistance.But, high-caliber thiourea has strong bad smell, additionally, the part in these additives such as thiourea, diphenylguanidine (DPG) and/or the casein for stabilizer are carcinogen and/or anaphylactogen.Although DPG provides generally longer than other accelerator hardening time and time of scorch, but reaction is still too fast.Additionally, the caseic use as the DPG of accelerator and as stabilizer is considered to have human health risk aspect ratio according to REACH-CLP unit in polymer composition, elastic composition or latex composition > 1.Therefore, the glove of casein containing protein and/or DPG are not needs for the problem that health is relevant.Additionally, substantial amounts of thiourea produces malodorous elements and is hypersensitive.It addition, hardening time and time of scorch, solidify start before can be of short duration by the time period that rubber composition carries out processing.
Therefore, it can for preparing the polymer composition of elastomeric article of thin, pliable and tough and that there is improvement hot strength, tear resistance and wear resistence, elastic composition or latex composition and the method for elastomeric article of thin, pliable and tough and that there is improvement hot strength and wear resistence and/or tear resistance can be prepared represent the progress of this area.
Summary of the invention
Disclosing in conjunction with at least one secondary accompanying drawing disclosed herein or describe polymer composition, elastic composition or latex composition, it comprises: the aqueous emulsion latex of at least one polyisoprene polymer；Comprise the first at least one accelerator of thiourea, thiazole or dialkyl dithiocarbamate or their combination；Comprise the second accelerator of thiuram or xanthogen or their combination；At least one vulcanizing agent；And activator, the total amount of wherein said first accelerator and the second accelerator is the polymer composition of 0.2PHR to 2.5PHR, elastic composition or latex composition, and described polymer composition, elastic composition or latex composition are without diphenylguanidine or casein, as set forth more completely in detail in the claims.From the description below with the accompanying drawing various advantages that present invention will become more fully understood and feature.
Accompanying drawing is sketched
In order to understand the mode of the features described above of the present invention in detail, it is possible to reference to embodiment, the present invention summarized briefly above is more particularly described, some of which embodiment is illustrated in accompanying drawing.It should be noted, however, that accompanying drawing illustrate only the present invention exemplary and can not it is taken as that be restriction on its scope because the present invention can allow other equivalent effective embodiment.Should be appreciated that the key element of an embodiment and feature can occur in other embodiments without statement further.It will be further understood that in the conceived case, identical accompanying drawing labelling is for representing the identical element having in figure.
Fig. 1 describes the flow chart of the method for compounding polymer composition according to one or more embodiments of the present invention, elastic composition and/or latex composition.
Fig. 2 describes the flow chart of the alternative method of compounding polymer composition according to one or more embodiments of the present invention, elastic composition and/or latex composition.
Fig. 3 describes the table of the exemplary formulation of the polymer composition, elastic composition and/or the latex composition that illustrate according to one or more embodiments of the present invention.
Fig. 4 describes the flow chart of the method preparing dipped article such as glove or condom according to embodiment of the present invention；And
Fig. 5 describes the following diagram according to embodiment of the present invention: immersed by model in polymer accelerator solution, described model is immersed in polymer composition, elastic composition and/or latex composition, form coating, optionally described coating immersed in one or more accelerator solution and produce glove.
Detailed Description Of The Invention
Embodiment of the present invention include polymer composition, elastic composition and/or latex composition, these compositionss form elastomeric article, as supported glove, without supporting glove and condom.Also include compounded composition according to embodiment of the present invention and manufacture have the method for this based article of physical property of improvement, particularly have the physical property of enhancing as significantly strengthen aging before and aging after tensile property and the glove of tear resistance and condom.According to embodiment of the present invention, described compositions includes novel polymer compositions, elastic composition and/or latex composition, and described novel polymer compositions, elastic composition and/or latex composition are without DPG and casein.
Polymer composition, elastic composition and/or latex composition comprise such as, natural polyisoprene or synthetic polyisoprenes.Such as, the water base polyisoprene emulsion of synthesis, such as there is high-cis Isosorbide-5-Nitrae content and high linearityIR401 formulation materials, such as comprises the admixture of polybutadiene and polystyrene.In some embodiments of the present invention, polymer composition, elastic composition or latex composition comprise also with trade markThe polybutadiene sold and the styrene block copolymer of polyisoprene.
Also comprise such as according to embodiment of the present invention, naturally occurring polyisoprene, the cis 1 of synthesis, 4-polyisoprene, carboxylated acrylonitrile butadiene, non-carboxylated acrylonitrile butadiene, itrile group butadiene, polychlorobutadiene, polyethylene, butyl latex, styrene-butadiene (SBR), styrene-butadiene latex, styrene-isoprene-phenylethene (SIS), styrene-ethylene/butylene-styrene (SEBS), styrene-acrylonitrile (SAN), polyethylene-propylene-diene, water base polyurethanes, the at least one of solvent-based polyurethanes or their combination or admixture.
Additionally, the isoprene rubber latex of natural isoprene rubber latex and synthesis produces flocculation (it is the gathering of polymer beads) inherently.The sulfuration evenly and completely assembling obstruction compositions of granule.It is not wishing to be bound by theory, think that the traditional rubber accelerator (such as having the caseic DPG as stabilizer) of the presulfurization being generally used for natural rubber latex and other synthetic rubber latex promotes the polymer beads short vulcanization assembled, outside is cured and internal keeps unvulcanized (because once outside cures, sulfur or other cross-linking agent cannot permeate the outside of sulfuration and arrive inside), cause that in bulk molecule, crosslinking and intermolecular cross-linking reduce, and thus produce the physical property of suboptimum.
The additive cross-linking isoprene molecule and provide chemical reaction, such as sulfur and zinc oxide also it is included as according to the polymer composition of the present invention, elastic composition and/or latex composition.
Also include having the polymer composition of at least two group accelerator, elastic composition and/or latex composition according to embodiment of the present invention, wherein the first accelerator is thiourea, thiazole and dialkyl dithiocarbamate or at least one of their combination；And the second accelerator comprises thiuram and xanthogen or their combination.Such as, polymer composition, elastic composition or latex composition comprise: wherein the total amount of accelerator is with the dry weight basis (PHR of polymer, number in each hundred parts of rubber) it is 0.2 weight % to 2.5 weight %, wherein thiourea comprises 0.2%-0.4%PHR.
Dialkyl dithiocarbamate according to the present invention includes SDD, PZ, (DDC)2Zn, zinc dibutyl dithiocarbamate, sodium diethyldithiocarbamate, NB sodium dibutyl dithiocarbamate, zinc dibenzyl dithiocarbamate and their combination.
Thiuram according to the present invention includes tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, Bis(pentamethylene)thiuram tetrasulfide and their combination.
Xanthogen according to the present invention includes many sulfuration diisopropyl xanthates, vulcanizes dialkyl xanthate, many dibutyl xanthogen disulfides ester and their combination more.
Thiazole according to the present invention includes mercaptobenzothiazoler, mercaptobenzothiazole zinc, dibenzothiazyl-disulfide, N-cyclohexyl time sulfonamido-2-[4-morpholinodithio, the N-tert-butyl group time sulfonamido-2-[4-morpholinodithio (TBBS), N-morpholino-sulfo--2-[4-morpholinodithio and their combination.
Thiourea according to the present invention includes N, N '-rhenocure CA (DPTU), N-phenyl N-cyclohexyl thiourea, N-phenyl-N-α-phenylethyl thiourea, N-phenyl-N '-ethyl thiourea, N-p-methoxyphenyl N '-ethyl thiourea and their combination.
Polymer composition, elastic composition and/or latex composition provide, in conjunction with a small amount of thiazole and using of thiourea accelerator, the time of scorch grown especially.In this article, the total amount meaning wherein accelerator on a small quantity is 0.2%PHR to 2.5%PHR.It addition, when do not use have as the DPG of the milk casein of stabilizer time, relatively long compositions working life is possible, thus in processing to manufacture the action pane phase adding compositions in the process of elastomeric article by described compositions.
Limited without wishing to by theoretical or operation mechanism, think that the thiazole using to combine on a small quantity and thiourea accelerator (such as novelly, TBBS and DPTU) make precuring speed and vulcanization reaction speed slow to the level that previous accelerator combination had not realized, i.e. longer time of scorch.Additionally, due to therefore sulfuration slows down, it is possible to adopt a series of polymer composition temperature, elastic composition temperature or latex composition temperature.This temperature according to appointment 20 DEG C to 35 DEG C make crosslink density optionally change as required to give different desired physical properties, thus make various compositions be able to " adjustment " and be served by for different.Because the amount of crosslink density can change, that is, the physical property such as tear resistance of resulting product (such as surgical glove, examination gloves, support glove, condom etc.) and significantly strengthen aging before and aging after hot strength be possible now.Without being bound by theory, it is believed that the sulfuration because DPTU and TBBS slows down, produce longer polysulfide (polysulfide) key, cause hot strength higher under relatively low crosslink density.
It is additionally considered that and uses the membrane structure of polymeric film, elastomer film or latex film that sulfur vulcanizes as cross-linking agent to be occurred by the mobility because of polymer chain in granule (in molecule) and between granule, sulfur-crosslinked between the polymer molecule of (intermolecular) is made.This film causing part presulfurization or coating, the film of described part presulfurization or coating can be formed on the mould (such as ceramic die, i.e. aluminosilicate, glass etc.) of the glove being dipped in polymer composition, elastic composition or latex composition or condom shape.Including making polymer composition, elastic composition or latex composition 20 DEG C of-35 DEG C of presulfurizations to obtain the acceptable degree of cross linking according to embodiment of the present invention, it is according to needing 10 hours to 20 hours in certain embodiments of the present invention.In at least one exemplary, about 20 hours is suitable.
The film being arranged on mould or coating are about 110 DEG C in temperature to the baking oven of 130 DEG C, carry out after cure.The character of crosslinking (crosslinking of short chain list sulfide and disulphide crosslinking and long-chain polysulphides crosslinking) and by crosslink type that the control (such as, shearing property) of the presulfurization degree in polymer composition, elastic composition or latex composition is formed between particles and post-treatment conditional decision membrane structure.
In addition, think that the use of as above TBBS and the DPTU providing long time of scorch also makes the sulfuration (cross-linking also referred to as periphery) of the outside of the flocculation of polymer flocculation, elastomer or flocculating latex slow down, thus promote the sulfuration of the inside of flocculation, it is provided that higher polymer architecture.In addition, think when polymer composition, elastic composition or latex composition are aging, the use of TBBS and DPTU promotes crosslinking, causing that hot strength further enhances, this makes the use of other accelerator (such as DPG) that hot strength reduces completely contradict with display in ageing process.Additionally, comprising about 0.2PHR to the thiazole accelerators of about 2.5PHR and the polymer composition of total amount of thiourea accelerator, elastic composition or latex composition is substantially less stink.And as it has been described above, such composition is also substantially less causes allergy.Fig. 3 describes the compositions of the amount describing various composition according to embodiment of the present invention, and the relative physical data compared to reference composition, described composition is for comprising some exemplary polymer compositionss of the dithiocar-bamate of various amount, xanthogen, thiourea, thiuram and/or thiazole, elastic composition and/or latex composition.As described below, it is possible to compounded polymer composition, elastic composition and/or latex composition.
As seen in Figure 3, the present invention without DPG and shockingly enhanced ultimate tensile strength (UTS) and tearing strength without caseic embodiment.Additionally, the working life of each embodiment is also considerably longer than comparison.At least one exemplary of the present invention include producing having at least 20MPa aging before UTS and after 70 DEG C of accelerated ageings 7 days at least 18MPa aging after Ultimate Tensile stretch the polymer composition of goods of tearing strength of intensity and 25N/mm, elastic composition or latex composition.
Polymer composition in Fig. 3 is generally of the viscosity of 250 centipoise-5000 centipoises and comprises conventional stabilizer, and described stabilizer includes but not limited to potassium hydroxide, ammonia, sulfonate etc..Described compositions can comprise other conventional component such as surfactant, antimicrobial, filler/additive, pigment etc..At least one embodiment of invention disclosed herein includes the compositions comprising filler and/or enhancing thing such as silicon dioxide, metal dust and ceramic powders, glass fibre etc. to provide grasp property, texture, intensity and other physical property.This type of filler and enhancing thing can such as comprise the material of 2 weight %-20 weight %.In other embodiments, filler and enhancing thing can comprise the 20 weight %-50 weight % various application for formulating according to final performance.Optionally add other additive as required as anti-flammability, resistance and electric arc retardancy, adhesion promoter, UV stable, hardness, pigment etc..
In certain embodiments of the invention, polymeric compositions, elastic composition and/or latex composition are foamed, in order to formed with the scattered air chamber of 5-50 percent by volume.When being arranged on model as coating using compositions, it is possible to form closed-chamber or open chamber, described in the common U.S. Patent No. 8,192,834, No.8,001,809 and No.7,814,571 transferred the possession of, it is by reference to be integrally incorporated herein.In certain embodiments of the invention, described room interconnects in polymer emulsion floor.Closed-chamber provides high pliable and tough, soft and spongiform liquid-proof build polymer emulsion coating, and provides good dry grasp property and wet skid.Closed-chamber is generally of the air content of 5-15 percent by volume.The open chamber interconnected is typically about 15-50 percent by volume and provides breathable article (that is, glove) by the polymer emulsion layer foamed.The polymer emulsion layer of this foaming can permeate the thickness of more than half in knitted interlining, although described polymer emulsion layer does not permeate whole thickness, thus substantially avoid and penetrates, i.e. avoids skin and contact with polymer emulsion.
Polymer composition can comprise extra surfactant as20 with stabilized latex foam.Once compositions with suitable air content foaming and is regulated viscosity, as well known for one of skill in the art by using impeller to carry out the refinement of foam with suitable speed.Bubble size can use different impeller to refine with the speed reduced.Whether foam, elastomer coating can be applied by the following method: by model or dress on it and have model in knitted interlining immerse in latex emulsion or spray on lining by coating, or for without supporting glove, model being directly immersed in latex emulsion or uses latex emulsion jet model.
The method preparing dipped article according to embodiment of the present invention as described below comprises the following steps: model immerses coagulant (such as, strength coagulant is calcium nitrate such as) in, described model is immersed in polymer composition, elastic composition or latex composition to form dipped article, such as surgical glove or examination gloves or condom.In certain embodiments of the invention, model is immersed weak coagulant such as weak acid (such as acetic acid or first aqueous acid).Then described goods optionally can be immersed in strength coagulant.It is not wishing to be bound by theory or limits, it is believed that the strength coagulant worked on outer layer promotes the fast gelation of outer layer, causes Surface hardened layer.The outer surface solidified prevents coagulant from migrating in the inside of rete or coating, causes the incomplete gelling of inside.In other words, the strength coagulant worked on the outer layer of film or coating promotes the fast gelation of outer layer, does not thus allow coagulant to arrive internal.It is thus possible, for instance the gelling of the inside of coating is incomplete.Or, weak acid promotes the gelling of the inside of film or coating, because during weak acid makes outer surface gelling lentamente and migrate to the inside of latex layer lentamente, causing more slowly and gelling completely.After immersing in weak acid, optionally described goods are immersed in strength coagulant so that outer surface hardens.
It is additionally considered that polymer molecule is more nearly and enhances such as when the inside more fully gelling making goods, zinc, zinc oxide or sulfur-crosslinked.Think that the enhancing cross-linked causes the enhancing of notable and unexpected wear resistence.As it has been described above, in certain embodiments of the invention, it is the application of strength coagulant (such as 2-15wt% calcium nitrate aqueous accelerator solution) after the application of weak acid.
Make polymer composition, elastic composition or latex composition described accelerator solution that is unstable and that condense comprise calcium nitrate, calcium chloride, sodium chloride, potassium chloride, aluminum chloride, aluminum sulfate and class saloid in one or more.These coagulant are highly soluble in water and are strength coagulants.It addition, the aqueous-based polymers coagulant coating (can produce the thickness of about 5 microns to 50 microns on model) for model described in application may be used in embodiment of the present invention.Polymer coagulant coating solution has suitable model surface wettability and enough viscosity or rheological properties, in order to form the thin layer of polymer coagulant coating.Realize at least one method of this purpose for wetting agent and viscosity modifier being added into polymer coagulant coating solution.
Polymer coagulant coating dries with rational speed, this provides the operating time section determined very much, within this time period, polymer coagulant coating keeps viscosity to accept to limit the application of the discrete coagulant granule of the size of required geometric error modeling of glove surface, shape and distribution.One exemplary polymer coagulant coating solution includes the polymer of copolymer or the derivant being selected from poly N-vinyl-2-Pyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylamide (PAC) and/or PVP, PVA, PAA or PAC.The amount of the polymer existed is about 0.1 to 10 dry weight percentage, and in certain embodiments of the invention, for about 0.5 to 1.5 dry weight percentage, described in the common U.S. Patent No. 7,814,570 transferred the possession of, it is by reference to be integrally incorporated herein.
Fig. 1 describes the flow chart of the method 100 of compounding polymer composition according to one or more embodiments of the present invention, elastic composition or latex composition.Method 100 starts from step 102 and carries out to step 104, now stirs the solution of polyisoprene in groove such as,Polyisoprene latex is (such as,IR-401B).In step 106, a sulphur content prose style free from parallelism (groove is still in stirring optionally together) is stirred into groove continues reasonable time.In step 108, stabilizer is mixed in groove about one hour.Method 100 carries out to step 110, now the inclusions polyisoprene latex of described groove, sulfur and stabilizer is heated about 30 minutes.
In step 112, optionally, deciding whether to add coloring agent such as titanium dioxide, it adds in step 114.Then method 100 carries out to step 116, now adds one or more accelerator, for instance thiazole and thiourea.According at least one embodiment of the present invention, described thiazole comprises TBBS and described thiourea comprises DPTU, and also dithiocar-bamate such as Bis(pentamethylene)thiuram tetrasulfide (DPTT) can be comprised, they will be added in groove and mix.In step 118, optionally, said mixture is cooled to such as 28 DEG C-32 DEG C.In step 120, optionally introduce a surfactant in described mixture.In step 122, optionally another kind accelerator such as dithiocar-bamate (such as (DDC)2Zn (ZDEC)) is mixed in groove.In step 124, optionally the chilled water of alkalization is mixed in described mixture.In step 126, antioxidant is mixed in groove, and in step 128, the solution of ammonium hydroxide is mixed in groove.In step 130, mixture is mixed a period of time.In step 132, method 100 terminates.
Fig. 2 describes the flow chart of the alternative method 200 of compounding polymer composition according to one or more embodiments of the present invention, elastic composition and/or latex composition.At least one illustrative methods of compounding compositions shown in Figure 3 is as follows.Method 200 starts from step 202.By a certain amount of without DPG and caseic polymer as comprised polyisoprene (such as,IR401B polymer/latex) Polymeric delivery to mixing channel, and in step 204 stir about 30 minutes together with a sulphur content prose style free from parallelism, and carry out to step 206, in mixing channel, now stir stabiliser solution.In step 208, it is possible to this mixture heated time of appropriate amount and makes it compounding or ripening about a hour, hereafter, appropriate accelerator such as thiuram dispersion being stirred in step 210.In step 212, activator is stirred in described mixture.In step 214, antioxidant is stirred in described mixture.In step 214, method 200 terminates.
At least one illustrative methods of compounding described compositions shown in Figure 4 is as follows.By a certain amount of isoprene (such as,IR401B polymer/latex) it is delivered to mixing channel and stirs.A sulphur content prose style free from parallelism is added to described groove and stir about 30 minutes, and introduces stabiliser solution.Compounding about one hour of described compositions and appropriate thiuram dispersion is made to be concomitantly introduced into together with titanium dioxide dispersion.Make described compositions compounding about one hour.Make described compositions ripening about 12 hours-60 hours, be stirred with 30 minutes intervals.
According at least one embodiment of the present invention, by the appropriate dithiocar-bamate such as NB sodium dibutyl dithiocarbamate (butyl of such as 5%) or at least one of (DDC)2Zn introduce in mixing channel, subsequently xanthogen polysulfide such as ROBACAS100 is introduced in mixing channel.Freezing alkalization water is optionally added into mixing channel.When the temperature of described compositions falls to approximately 22 DEG C, the antioxidant methylmercaptobenzimidazole dispersion of soft water and ammonia is slowly mixed together.Appropriate titanium dioxide dispersion (such as RaloxLC), potassium octanoate (such as Alkon8627) and/or the phenylethylene/maleic anhydride copolymer (the Scripset550 solution of such as 5%) with the esterification of low-molecular-weight second butyl ester are introduced mixing channel and stir.
Fig. 4 describes the flow chart of the method 300 preparing dipped article such as glove or condom according to embodiment of the present invention.In certain embodiments, each step of method 300 is carried out.In other embodiments, omit or skip some step.Method 300 starts from step 301 and carries out to step 302, where a determination is made whether pre-thermal model.If answer is affirmative, in step 303 by model heating to such as 50 DEG C-60 DEG C.If answer is negative, method 300 proceeds directly to step 304, now model such as glass model or ceramic model is immersed in the groove with coagulant.In step 306, model is taken out from groove, dry at such as 30 DEG C-60 DEG C about 1-5 minute.In step 308, model is immersed in the groove with polymer composition as above, elastic composition or latex composition, and coating is formed on model with the shape of goods.
In step 310, the model with the first elastomer coating being arranged on model is immersed and the groove with coagulant (such as, comprising strong acid or weak aqueous acid) continues several seconds to a few minutes.In some embodiments of the present invention, described weak acid is the solution of acetic acid.In step 312, will immerse while there is the model option of the coating being arranged on model strength coagulant such as calcium citrate, calcium nitrate, or immerse in another coagulant well-known to those skilled in the art, then take out.In step 314, decide whether to increase by the second coating on described first elastomer coating.If answer is affirmative, method 300 is back to step 308.It addition, no matter whether described ground floor is foaming or does not foam, described second coating can be foaming or not foam, and vice versa.If not increasing by the second coating, method 300 carries out to step 316.In step 316, making glove such as, at 35 DEG C-50 DEG C, optionally leaching impurity and protein continue about 1-3 minute in aqueous.In step 318 so that glove dry in atmosphere.In step 320, glove are placed in baking oven and solidify, for instance at 80 DEG C-100 DEG C, continue 30 minutes to 40 minutes.In step 322, method 300 terminates.
Fig. 5 describes the following diagram 500 according to embodiment of the present invention: immersed by model in polymer accelerator solution, described model is immersed in polymer composition, elastic composition and/or latex composition, form coating, optionally described coating immersed in one or more accelerator solution and produce glove.In Figure 5, generally illustrating the schematic diagram of processing line, wherein model 504 such as hand model immerses in groove 506, forms polymer coagulant coating 502 on model 504.The model 504 with the polymer coagulant coating 502 being arranged on model 504 is taken out from groove 506.The model 504 with the polymer coagulant coating 502 being arranged on model 504 is optionally made to dry, and it is subsequently dipped in the polymer composition in groove 512, elastic composition and/or latex composition 510, model 504 is formed the coating of compositions 510.Being delivered to by model 504 in the groove 516 comprising accelerator solution 518 (such as weak coagulant such as acetic acid, formic acid etc.) subsequently, described weak coagulant promotes the slow gelling of coating of compositions 510.Optionally make the accelerator solution 518 in the coating of the compositions 510 on model 504 dry and immerse to comprise strength coagulant 522 in the groove 524 of calcium nitrate, as described herein.Then optionally make the model 504 being provided with above-mentioned strength coagulant on model 504 dry and immerse in the groove 528 comprising polymer composition, elastic composition and/or latex composition 526, described compositions can be identical or different compared with the polymer composition in groove 512, elastic composition and/or latex composition, can be maybe such as, the compositions of foaming.Washing station (not shown) can be polymer composition, elastic composition and/or latex composition leaching impurity.Heating station (not shown) such as baking oven makes the polymer coating being arranged on hand model 504, elastomer coating and/or latex curing of coatings to form glove 530.Glove are peeled off from model 504 and optionally make glove 530 overturn by waste station (not shown).
Other use referring to word described in term "/a kind of (a) " and " one/a kind of (an) " and " described/should (the) " and embodiment of the present invention be interpreted as odd number and plural both, except as otherwise noted or otherwise clearly contradicted.Numerical range herein is intended only to serve as the method for simplifying relating to falling into each independent numerical value in scope；Unless otherwise indicated herein, and each value range is incorporated in description, as individually recorded herein.All methods as herein described can be implemented in any suitable order, unless otherwise indicated herein or otherwise clearly contradicted.The use of any embodiment provided herein and all embodiments or exemplary language (such as, " such as (suchas) ") is merely intended to be better described the present invention, and the scope of the present invention is not caused restriction, unless stated otherwise.Language in description should not be construed as and shows that any key element not being claimed is implement the key of the present invention.Although using some embodiments and exemplary drawings to there is described herein the present invention by way of example, those skilled in the art will recognize the present invention and being not limited to the embodiment of accompanying drawing or described accompanying drawing.
Title used herein only for layout purpose, is not intended to the scope for limiting description or claims.As the application in the whole text use, word " can/be likely to " uses with permissive sense (namely representing likely), rather than to force meaning (namely representing necessary) use.Similarly, word " including/comprise (include) ", " including/comprise (including) " and " including/comprise (includes) " means to include, but are not limited to.Word " glove " means glove or glove liner.Term dispersion, emulsion and compositions can also use used interchangeably herein.
All scopes described herein include value therebetween and can include or not include end points.The scope optionally included is from integer value (or including an origin endpoint) therebetween, and it is in the described order of magnitude or order of magnitude lower.Such as, if lower limit is 0.2, the end points optionally comprised can be 0.2,0.3,0.4 ... 1.1,1.2 etc., and 1,2,3 etc.；If higher limit is 8, the end points optionally included can be 7,6 etc., and 7.9,7.8 etc..The border of side such as more than 3, includes the continuum boundary (or scope) started with the integer value of the described order of magnitude or order of magnitude lower similarly.Such as, more than 3 include more than 4, or more than 3.1.
Although several exemplary of the present invention described in detail above, when it will be apparent to one skilled in the art that substantially without departing substantially from teachings disclosed herein, can there be many changes in embodiments.These type of changes any and all are intended to be contained in embodiment of the present invention, and when without departing substantially from the scope of the present invention, it is possible to find out other embodiment, and the scope of the present invention is determined by the claims below.It will thus be appreciated that accompanying drawing and detailed description thereof are not intended as limiting the present invention in particular forms disclosed, on the contrary, the present invention contains all equivalents and replacement scheme that fall in the spirit and scope of the present invention as defined by the appended claims.
Claims (15)
1. polymer composition, elastic composition or latex composition, it comprises:
The aqueous emulsion of polyisoprene polymer；
First accelerator, it comprises at least one of thiourea, benzothiazole sulfenamide, thiazole or dialkyl dithiocarbamate or their combination；
Second accelerator, it comprises thiuram or xanthogen or their combination；
At least one antioxidant；
At least one vulcanizing agent；And
Activator；
The total amount of wherein said first accelerator and described second accelerator is the polymer composition of 0.2PHR to 2.5PHR, elastic composition or latex composition, and described polymer composition, elastic composition or latex composition are substantially free of diphenylguanidine and/or casein.
2. polymer composition as claimed in claim 1, elastic composition or latex composition, wherein said dialkyl dithiocarbamate is at least one of SDD, PZ, (DDC)2Zn, zinc dibutyl dithiocarbamate, sodium diethyldithiocarbamate, NB sodium dibutyl dithiocarbamate, zinc dibenzyl dithiocarbamate or their combination.
3. polymer composition as claimed in claim 1, elastic composition or latex composition, wherein said thiuram is at least one of tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, Bis(pentamethylene)thiuram tetrasulfide or their combination.
4. polymer composition as claimed in claim 1, elastic composition or latex composition, wherein said xanthogen is many sulfuration diisopropyl xanthates, vulcanizes dialkyl xanthate, many dibutyl xanthogen disulfides ester or their combination more.
5. polymer composition as claimed in claim 1, elastic composition or latex composition, wherein said thiazole is mercaptobenzothiazoler, mercaptobenzothiazole zinc, dibenzothiazyl disulfide or their combination.
6. polymer composition as claimed in claim 1, elastic composition or latex composition, wherein said benzothiazole sulfenamide is N-cyclohexyl time sulfonamido-2-[4-morpholinodithio, the N-tert-butyl group time sulfonamido-2-[4-morpholinodithio (TBBS), N-morpholino-sulfo--2-[4-morpholinodithio or their combination.
7. polymer composition as claimed in claim 1, elastic composition or latex composition, wherein said thiourea is N, N '-rhenocure CA (DPTU), N-phenyl N-cyclohexyl thiourea, N-phenyl-N-α-phenylethyl thiourea, N-phenyl-N '-ethyl thiourea, N-p-methoxyphenyl N '-ethyl thiourea or their combination.
8. polymer composition as claimed in claim 1, elastic composition or latex composition, it also comprises natural polyisoprene, the cis 1 of synthesis, 4-polyisoprene, carboxylated acrylonitrile butadiene, non-carboxylated acrylonitrile butadiene, itrile group butadiene, polychlorobutadiene, polyethylene, butyl latex, styrene-butadiene (SBR), styrene-butadiene latex, styrene-isoprene-phenylethene (SIS), styrene-ethylene/butylene-styrene (SEBS), styrene-acrylonitrile (SAN), polyethylene-propylene-diene, water base polyurethanes, solvent-based polyurethanes or their admixture.
9. polymer composition as claimed in claim 1, elastic composition or latex composition, wherein said polymer composition, elastic composition or latex composition comprise the TBBS of the DPTU and about 0.2PHR to 0.4PHR of about 0.2PHR.
10. glove, it comprises:
The polymer coating of hand, elastomer coating or latex coating,
Wherein said polymer coating, elastomer coating or latex coating comprise:
The aqueous emulsion of polyisoprene polymer；
First accelerator, it comprises at least one of thiourea, benzothiazole sulfenamide, thiazole or dialkyl dithiocarbamate or their combination；
Second accelerator, it comprises thiuram or xanthogen or their combination；
At least one antioxidant；
At least one vulcanizing agent；And
Activator；
The total amount of wherein said first accelerator and the second accelerator is the polymer composition of 0.2PHR to 2.5PHR, elastic composition or latex composition, and described polymer composition, elastic composition or latex composition are substantially free of diphenylguanidine and/or casein.
11. glove as claimed in claim 10, wherein said glove have at least 20MPa aging before ultimate tensile strength and/or after 70 DEG C of accelerated ageings 7 days at least 18MPa aging after ultimate tensile strength and the minimum tearing strength of 25N/mm.
12. the method preparing polymer product, elastomeric article or latex product, comprising:
Model is immersed in coagulant；
Described model is immersed in polymer composition, elastic composition or latex composition, polymer coating, elastomer coating or latex coating are thus set on described model；
Described polymer coating, elastomer coating or latex coating are immersed at least one of weak acid or strength coagulant；And
Allowing described polymer coating, elastomer coating or latex coating to dry, wherein said model is hand model or condom model, is consequently formed the nothing without powder and supports glove or condom.
13. method as claimed in claim 12, wherein said polymer composition, elastic composition or latex composition also comprise natural polyisoprene, the cis 1 of synthesis, 4-polyisoprene, carboxylated acrylonitrile butadiene, non-carboxylated acrylonitrile butadiene, itrile group butadiene, polychlorobutadiene, polyethylene, butyl latex, styrene-butadiene (SBR), styrene-butadiene latex, styrene-isoprene-phenylethene (SIS), styrene-ethylene/butylene-styrene (SEBS), styrene-acrylonitrile (SAN), polyethylene-propylene-diene, water base polyurethanes, solvent-based polyurethanes or their combination or admixture.
14. method as claimed in claim 12, it is further comprising the steps of: makes the presulfurization at 20 DEG C-35 DEG C of described polymer composition, elastic composition or latex composition, and obtains the required degree of cross linking when being no faster than about 20 hours.
15. method as claimed in claim 14, it is additionally included at the temperature of 110 DEG C-150 DEG C and makes the step without support glove or condom after cure without powder.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361904267P | 2013-11-14 | 2013-11-14 | |
| US61/904,267 | 2013-11-14 | ||
| PCT/AU2014/001040 WO2015070276A1 (en) | 2013-11-14 | 2014-11-14 | Polymeric compositions comprising polyisoprene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105722908A true CN105722908A (en) | 2016-06-29 |
Family
ID=53042369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480059749.1A Pending CN105722908A (en) | 2013-11-14 | 2014-11-14 | Polymeric compositions comprising polyisoprene |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20150128329A1 (en) |
| EP (1) | EP3068833A4 (en) |
| CN (1) | CN105722908A (en) |
| AU (1) | AU2014351059A1 (en) |
| WO (1) | WO2015070276A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110121320A (en) * | 2016-10-14 | 2019-08-13 | 海德鲁格莱德涂料有限责任公司 | Hydrophilic polymer coating with durable lubricity |
| CN111032765A (en) * | 2017-08-25 | 2020-04-17 | 日本瑞翁株式会社 | Latex composition |
| CN114261046A (en) * | 2021-12-10 | 2022-04-01 | 成都盛帮密封件股份有限公司 | Lamination method of multifunctional latex glove composite surface |
| CN114846067A (en) * | 2019-12-20 | 2022-08-02 | 丘奇和德怀特有限公司 | Polymer compositions and products formed therefrom |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201514234A (en) | 2013-07-16 | 2015-04-16 | Skinprotect Corp Sdn Bhd | Elastomeric film-forming compositions and articles made from the elastomeric film |
| US11925221B2 (en) | 2013-07-22 | 2024-03-12 | Summit Glove Inc. | Protective device for use with a glove having textured grip |
| US20230301374A1 (en) * | 2013-07-22 | 2023-09-28 | Summit Glove Inc. | Protective device for use with a glove |
| US11925222B2 (en) * | 2015-06-19 | 2024-03-12 | Summit Glove Inc. | Safety glove with fingertip protective member |
| US10154699B2 (en) | 2015-09-10 | 2018-12-18 | Ansell Limited | Highly chemical resistant glove |
| CA3236599A1 (en) | 2015-10-18 | 2017-04-27 | Allegiance Corporation | Water-based hydrogel blend coating and method of application to elastomeric articles |
| JP6769445B2 (en) * | 2016-01-27 | 2020-10-14 | 日本ゼオン株式会社 | Latex composition |
| MY193512A (en) | 2017-02-22 | 2022-10-17 | Zeon Corp | Latex composition |
| US20190069618A1 (en) * | 2017-09-06 | 2019-03-07 | Handgards, Inc. | Embossed gloves with gripping features |
| US10759913B2 (en) | 2017-12-13 | 2020-09-01 | Allegiance Corporation | Vulcanization composition for reducing allergenic potential and elastomeric articles formed therewith |
| CA3161886A1 (en) * | 2019-12-20 | 2021-06-24 | Church & Dwight Co., Inc. | Polymer compositions and products formed therewith |
| US20210337930A1 (en) * | 2020-04-29 | 2021-11-04 | UA Thomas Co. Ltd. | Slip resistant shoe cover |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1840573A (en) * | 2005-03-28 | 2006-10-04 | 东海橡胶工业株式会社 | Vibration damping rubber composition |
| CN1856537A (en) * | 2003-09-24 | 2006-11-01 | R.T.范德比尔特公司 | Accelerator system for synthetic polyisoprene latex |
| CN101395013A (en) * | 2006-03-03 | 2009-03-25 | 倍耐力轮胎股份公司 | Tyre and crosslinkable elastic composition |
| CN101410030A (en) * | 2005-12-01 | 2009-04-15 | 安塞尔保健产品有限责任公司 | Glove with hand-friendly coating and method of making |
| US20090209699A1 (en) * | 2008-02-20 | 2009-08-20 | Weinreich Hajo | Method of producing a rubber composition |
| CN101970548A (en) * | 2008-03-14 | 2011-02-09 | 忠诚股份有限公司 | Water-based resin composition and articles made therefrom |
| CN102164516A (en) * | 2008-05-01 | 2011-08-24 | 安塞尔保健产品有限责任公司 | Dip-formed synthetic polyisoprene latex articles with improved intraparticle and interparticle crosslinks |
| CN102604304A (en) * | 2009-03-19 | 2012-07-25 | 上海生大医保股份有限公司 | Method for preparing gloves and relevant products from polyisoprene aqueous emulsion |
| CN102643458A (en) * | 2012-05-12 | 2012-08-22 | 蔡瑞琳 | Mixed latex with antianaphylaxis |
| CN103025514A (en) * | 2010-06-25 | 2013-04-03 | 忠诚股份有限公司 | Vulcanization composition having reduced allergenic potential |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1055442A (en) * | 1963-07-24 | 1967-01-18 | Unilever Ltd | Improvements in reinforced rubber |
| US4012332A (en) * | 1974-01-30 | 1977-03-15 | American Cyanamid Company | Rubber vulcanization accelerator composition |
| US6618861B2 (en) * | 2000-12-28 | 2003-09-16 | Microflex Corporation | Medical gloves with watch viewing capabilities |
| US20030161975A1 (en) * | 2002-02-27 | 2003-08-28 | Lucas David M. | Polyisoprene condom |
| US7041746B2 (en) * | 2003-09-24 | 2006-05-09 | R.T. Vanderbilt Company, Inc. | Accelerator system for synthetic polyisoprene latex |
| RU2397184C2 (en) * | 2005-08-05 | 2010-08-20 | Кратон Полимерз Рисёч Б.В. | Rubber accelerator composition |
| EP2020427A1 (en) * | 2007-08-03 | 2009-02-04 | Ampelos | Glove and process for manufacturing the same |
| CN102712178A (en) * | 2010-01-22 | 2012-10-03 | 忠诚股份有限公司 | Methods for packaging and sterilizing elastomeric articles, and packaged elastomeric articles produced thereby |
-
2014
- 2014-11-12 US US14/539,354 patent/US20150128329A1/en not_active Abandoned
- 2014-11-14 AU AU2014351059A patent/AU2014351059A1/en not_active Abandoned
- 2014-11-14 EP EP14861918.2A patent/EP3068833A4/en not_active Withdrawn
- 2014-11-14 WO PCT/AU2014/001040 patent/WO2015070276A1/en active Application Filing
- 2014-11-14 CN CN201480059749.1A patent/CN105722908A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1856537A (en) * | 2003-09-24 | 2006-11-01 | R.T.范德比尔特公司 | Accelerator system for synthetic polyisoprene latex |
| CN1840573A (en) * | 2005-03-28 | 2006-10-04 | 东海橡胶工业株式会社 | Vibration damping rubber composition |
| CN101410030A (en) * | 2005-12-01 | 2009-04-15 | 安塞尔保健产品有限责任公司 | Glove with hand-friendly coating and method of making |
| CN101395013A (en) * | 2006-03-03 | 2009-03-25 | 倍耐力轮胎股份公司 | Tyre and crosslinkable elastic composition |
| US20090209699A1 (en) * | 2008-02-20 | 2009-08-20 | Weinreich Hajo | Method of producing a rubber composition |
| CN101970548A (en) * | 2008-03-14 | 2011-02-09 | 忠诚股份有限公司 | Water-based resin composition and articles made therefrom |
| CN102164516A (en) * | 2008-05-01 | 2011-08-24 | 安塞尔保健产品有限责任公司 | Dip-formed synthetic polyisoprene latex articles with improved intraparticle and interparticle crosslinks |
| CN102604304A (en) * | 2009-03-19 | 2012-07-25 | 上海生大医保股份有限公司 | Method for preparing gloves and relevant products from polyisoprene aqueous emulsion |
| CN103025514A (en) * | 2010-06-25 | 2013-04-03 | 忠诚股份有限公司 | Vulcanization composition having reduced allergenic potential |
| CN102643458A (en) * | 2012-05-12 | 2012-08-22 | 蔡瑞琳 | Mixed latex with antianaphylaxis |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110121320A (en) * | 2016-10-14 | 2019-08-13 | 海德鲁格莱德涂料有限责任公司 | Hydrophilic polymer coating with durable lubricity |
| CN110121320B (en) * | 2016-10-14 | 2022-06-03 | 海德鲁格莱德涂料有限责任公司 | Hydrophilic polymer coating with long-lasting lubricity |
| CN111032765A (en) * | 2017-08-25 | 2020-04-17 | 日本瑞翁株式会社 | Latex composition |
| CN114846067A (en) * | 2019-12-20 | 2022-08-02 | 丘奇和德怀特有限公司 | Polymer compositions and products formed therefrom |
| CN114261046A (en) * | 2021-12-10 | 2022-04-01 | 成都盛帮密封件股份有限公司 | Lamination method of multifunctional latex glove composite surface |
Also Published As
| Publication number | Publication date |
|---|---|
| US20150128329A1 (en) | 2015-05-14 |
| EP3068833A1 (en) | 2016-09-21 |
| EP3068833A4 (en) | 2017-09-13 |
| WO2015070276A1 (en) | 2015-05-21 |
| AU2014351059A1 (en) | 2016-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105722908A (en) | Polymeric compositions comprising polyisoprene | |
| CA2408626C (en) | Polyisoprene articles and process for making the same | |
| JP5137831B2 (en) | Latex accelerating composition | |
| JP4820412B2 (en) | Latex accelerator composition | |
| AU2006209226B2 (en) | Thin walled polynitrile oxide crosslinked rubber film products and methods of manufacture thereof | |
| JP2015094038A (en) | Manufacturing method of glove | |
| MXPA06003355A (en) | Accelerator system for synthetic polyisoprene latex. | |
| EP1482009B1 (en) | Elastromeric composition and process for producing glove having interpenetrating network structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20190104 |
|
| AD01 | Patent right deemed abandoned |