CN1078123C - Acrylic emulsion coatings for rubber articles - Google Patents

Acrylic emulsion coatings for rubber articles Download PDF

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Publication number
CN1078123C
CN1078123C CN96192822A CN96192822A CN1078123C CN 1078123 C CN1078123 C CN 1078123C CN 96192822 A CN96192822 A CN 96192822A CN 96192822 A CN96192822 A CN 96192822A CN 1078123 C CN1078123 C CN 1078123C
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multipolymer
monomer
acrylic emulsions
weight
composition
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CN1179745A (en
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I·里
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Avery Dennison Corp
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Avery Dennison Corp
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Priority claimed from US08/388,030 external-priority patent/US5691069A/en
Priority claimed from US08/486,948 external-priority patent/US5712346A/en
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Publication of CN1179745A publication Critical patent/CN1179745A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/14—Dipping a core
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

The present invention provides powder-free polymer coated rubber articles, particularly rubber gloves, coated with a non-tacky acrylic based emulsion copolymer formed by polymerization of at least one low surface energy monomer, at least one alkyl acrylate and at least one hard monomer. The copolymers are preferably formed by sequential polymerization. This provides improved properties versus the conventional manner for manufacturing rubber gloves involving dipping a mold in the shape of the article to be formed into a coagulant slurry containing calcium nitrate and calcium carbonate.

Description

The acrylic emulsion coatings that is used for rubber item
Technical field
The present invention relates to the thin-gage goods that formed by natural rubber or synthetic rubber, having one deck on the described rubber, not have powder polymer coated, and this coating becomes the detachability of mould or ground and wearing property (donning) may or to strengthen to some extent.
Background technology
The rubber item of being made by natural rubber or synthetic rubber comprises surgical glove, doctor's latex examination gloves, mitt, condom, catheter, balloon, gum rubber tubing, film etc.Some this based article, especially gloves need (donning) ability that wears, and promptly rubber item is in the surperficial sliding ability that goes up and slide and do not have excessively adhesion or rub of skin (tissue).Surgical glove needs to wet and wears ability, promptly slip over the ability on moist skin surface when the doctor checks, and mitt needs the ability that slips over the dry skin surface.Other rubber item such as catheter and gum rubber tubing need some and make rubber and body fluid and organize isolated method.
Although the present invention relates to be used for the polymer coated of all rubber items, will concentrate on the gloves, because from using and manufacture view, gloves are the most complicated rubber items.
In order to reach qualified wearing property, must the rubber surface of the gloves that contact with skin or tissue be improved to reduce friction.
Surgical glove as the surgical glove in modern times, requires its wear surface enough hydrophilic, absorbs the moisture that may exist on skin or the tissue surface when wearing with these goods of box lunch.Hydrogel coating has been used to reach this performance, US3 for example, and disclosed in 813,695, it is for reference to be incorporated into this paper.
By contrast, the gloves of inspection and other purposes do not have the wetting ability requirement, slip over skin (tissue) surface and the little ability of resistance or frictional force but still require this rubber item to have.
Traditionally, this point can reach by talcum powder or other powder material such as modified corn starch are coated on the surface that contacts with skin or tissue.Talcum powder can not re-use, and other powder can pollute the work area.The gloves that use for workman in the dustfree environment also are identical, the manufacturing environment of described dustfree environment such as computer chip and other electronic component.
With reference to figure 1, the general method of making rubber gloves is to contain the solidifying in the slurry of nitrocalcite and lime carbonate with mould immersion that is the article shape that will form is a kind of.After the drying, this mould is immersed rubber latex (latex) for some time, be enough to the coating that rubber is solidified and form desired thickness during this period of time.Make the rubber item baking oven that solidifies of formation vulcanize, cool off, immerse in the starch slurry then.Make the surface drying that scribbles starch so that one deck powder coating to be provided.After the cooling, rubber item is taken off from mould.This step is routed up gloves inside.Mould is cleaned and recycling.
Can and often the water leaching be used as the step of removing rubber impurity.
Make the US3 that the method for gloves and material also are disclosed in people such as Kavalier for example, 411,982 and 3,286, in 011, it is for reference that these two patents are incorporated into this paper, in " elastomerics " 17-20 page or leaf in August, 1979 people such as Sadowski " polyurethane rubber latex that is used for coagulating dip " to be incorporated into this paper for reference, and in " natural rubber technical bulletin " " flooding " of people such as Pendle with natural rubber latex also to be incorporated into this paper for reference.
Halogenide for example muriate and other chemical surface treatment agent has been used to eliminate for can driedly wearing the demand of coating powders coating on the finished product.Although effectively, this step expense is high and have and reduce the rubber item shortcoming of storage time.Desirable providing a kind ofly has not by no wearing property of the powder surface of high cost and has the rubber item of current popular goods aging.The storage time that this can significantly reduce manufacturing cost and prolong rubber item.
The US4 of Joung, 302,852 to be incorporated into this paper for reference, and this patent suggestion makes RTV silicon coating and gloves internal surface covalent attachment after the rubber surgical glove forms.It is said that this method has reduced the demand of wearing property powder but do not eliminate this demand.
Be the US4 of Joung equally, 304,008 to be incorporated into this paper for reference, and this patent is coated to covalently bound siloxanes or urethane on the outside surface of gloves, and makes the halogenation of gloves internal surface.This halogenated internal surface has been eliminated the demand to wearing property powder.
Be the US4 of Joung equally, 310,928 to be incorporated into this paper for reference, and this patent points out to replace coming from fat compound (lipoid or lipophilic substance) powder of mineral, in solidification liquid, combine the back and deposit, thereby solidifying formation one deck uniform thin film on the glove mould that rubber is arranged with tensio-active agent.This fat compound and tensio-active agent can be taken off the gloves of formation from its mould.
These suggestions and other suggestion do not obtain industrial approval.
Summary of the invention
The invention provides and cover and stick to securely rubber article, and can partly be absorbed into the acrylic copolymer on the rubber article, described rubber item carries out moulding by solidification on described acrylic copolymer.This multipolymer also can be deposited on the preformed rubber item.For example for gloves and other rubber item, this multipolymer impels formed rubber item to produce release property effectively and need not further chemical treatment and produce wearing property.By identical or different acrylic copolymer is deposited to the relative two sides of the rubber item that forms (as gloves), just can reach and do or wet wearing property and release property.
Acrylic copolymer is the multipolymer that is formed by at least a reactive low surface energy monomer (preferred siloxane oligomer), at least a alkyl acrylate and at least a reactive hard monomer copolymerization of emulsion-type preferably, and all the amount of hard monomers should be enough to directly or the mixing by multipolymer forms a kind of sticking multipolymer.This multipolymer preferably shows at least one main second-order transition temperature (Tg) peak more than 0 ℃ and generally at least one is lower than about 0 ℃ main second-order transition temperature peak.A kind of effective second-order transition temperature is preferably about 60 ℃ of about 15-usually above about 15 ℃.At present preferably at least wearing property surface form by making two monomer system sequential polymerization: an individual system provides low main second-order transition temperature peak, and another system provides high main second-order transition temperature peak.
But the multipolymer that preferably is used at present with mould separating is siloxane oligomer, butyl acrylate, methyl acrylate, methacrylic acid, vinylformic acid and the cinnamic multipolymer that contains copolymerization.
The multipolymer that preferably is used at present dried wearing property of temperature is the multipolymer that contains siloxane oligomer, vinylbenzene, butyl acrylate, methyl acrylate, vinylformic acid, TMPTA and n-isobutoxy Methacrylamide.
With regard to the efficient of emulsion polymerization, emulsion copolymers is made into highly filled emulsion.Highly filled is not that preparation coating is needed.Therefore, emulsion dilution can be contained with formation that 3% whole acrylic emulsions multipolymers, its solids content typical case to about 10% (weight), preferred about 6% (weight) that have an appointment is used to apply mould and the solids suspension of deposited coatings on formed rubber article.In another alternative plan, can be from emulsion acrylic acid class emulsion copolymers, after this carry out resuspending.
This suspension is used in combination with water-soluble polyvalent metal salt, and described metal-salt plays the effect of rubber latex peptizer.This peptizer can be deposited on the acrylic copolymer or therewith and deposit from suspension.Purpose provide a kind of make the peptizer salt surface concn that can in the time of industrial permission, solidify of sedimentary latex on copolymer coated.Preferred peptizer salt is nitrocalcite, and its working concentration is about at the most 40%, preferred about 20% to about 40% of a suspension weight.
In the manufacturing of goods, especially gloves, the mould with the surface that has applied peptizer and polymkeric substance is dipped in rubber latex or the latex, and rubber deposits and be solidified to the surface of multipolymer from this rubber latex or latex, forms the gloves internal surface that applies.With rubber item drying, the sulfuration that forms, immerse then in the aqeous suspension that shows the good identical or different acrylic copolymer of wearing property.Impregnation steps has formed wearing property polymeric coating on the outside surface of rubber gloves.The gloves through applying that will form are then taken off from mould.This step makes the gloves counter-rotating, and wearing property coating is placed on gloves inside.As well-known, purification can be adopted the water leaching effectively for rubber.
In implementation process of the present invention, preferred mould is a curve mold.Although can use ceramic or the mould on porcelain surface and the mould that has the fluorocarbon coating with high polish structure, but preferred employing is that the texture that is had is enough to make sedimentary layered article to produce the mould of matt finish, and described sedimentary layered article forms by rubber is deposited to copolymer coated going up from latex.Matt finish is by reaching the die surface roughen with sand or granulated glass sphere sandblast.Through measuring, the roughness on the surface of adopting is to paddy 8-10 micron approximately by the peak.
The wearing property surface and the release surface that preferably identical multipolymer are used for gloves, the side that wears of gloves contains W-Gum and a small amount of oil, the solid of promptly about 0.1% weight.
The skin friction force that preferred multipolymer is had require average out to about 0.05 pound to less than about 0.3 pound, be preferably about 0.2 to about 0.25 pound, so that the heavy slide plate of 200g can move on the surface that scribbles multipolymer of rubber item.
Brief Description Of Drawings
Fig. 1 is the schema of existing manufacturing rubber gloves method;
Fig. 2 is dsc (DSC) curve of hot-fluid-temperature function, performance be the copolymer coated second-order transition temperature peak of the preferred demoulding of the present invention; And
Fig. 3 is the dsc function curve of hot-fluid as the function of temperature, performance be the second-order transition temperature peak of preferably wearing property multipolymer of the present invention.
Describe in detail
Cannot not the invention provides stickingly acrylic copolymer, adhere to this copolymer aggressivity rubber And the surface of other goods is flexible copolymer coated to form, this coating can stretch and not with its Accompanying rubber surface separates. This copolymer is (excellent by at least a reactive low-surface-energy monomer But elect the siloxane oligomer of one or more copolymerization as), at least a alkyl acrylate and extremely Few a kind of hard monomer forms. This copolymer provides and has shown excellent release property and dried wearing property No powder coated rubber, and the protective finish that is used for other goods is provided.
Term used herein " rubber " refers to be made by natural rubber and/or synthetic rubber Goods. They generally deposit on the multivalent metal salt by solidifying from latex.
Term " but low-surface-energy monomer of copolymerization " is in case refer to by homopolymerization then only need a small amount of power will Monomer under this homopolymers removes from its coated surface. In the copolymer, but the low-surface-energy of copolymerization Monomer reduced with copolymer from the surface (no matter being mould, tissue or skin) except under energy.
But responding property siloxanes, carbon that typical copolymerization low-surface-energy monomer can be mentioned are fluoridized and are closed Thing and fatty acid ester and analog, with vinyl, acrylic acid and/or metering system acid functional group The low-surface-energy monomer. But the siloxane oligomer of copolymerization preferably.
Term used herein " but siloxane oligomer of copolymerization " refers to acrylate, first Siloxanes and the siloxanes of the polymerization of base acrylate or vinyl-functional include but not limited to third The olefin(e) acid polysiloxanes. Acrylate, methacrylate or vinyl functionality are at least 1, Be preferably 2 to about 3.
What but typical copolymerized siloxanes oligomer can be mentioned has by Hopewell, the Tegro that the Goldschmidt chemical company of Virginia makes and sellsSiloxanes acrylate RC149, 300,450,710,720 and 802 and ZMR1395, these polymer are many acrylate The line style dimethyl polysiloxane of sense, its molecular weight is between about 1, and 000-20 is between the 000g/mol. They comprise the product of dimethyl polysiloxane and pentaerythritol triacrylate. Can also carry The siloxane systems that arrives is made and is sold such as the GE siloxanes branch by General electronics corporation GE 6000 (a kind of vinyldimethicone) and 6010 catalyst concentrates. Also can The polysiloxanes that use is replaced by ethyoxyl.
With the weighing scale of the monomer that consists of acrylic copolymer, but copolymerization low-surface-energy monomer (also But and be preferably the copolymerized siloxanes oligomer) working concentration about 20% for about 0.7%-, excellent Elect about 1%-about 15% as. Their effect is to realize doing wet wearing property and promote the demoulding.
All the other monomers are selected the adhesion to the latex surface that provides good, and wearing property is (wet And do), good sense of touch, release property, and a kind of remarkable glass transition temperature (Tg) is provided Be at least about 15 ℃, be preferably the about 60 ℃ not sticking copolymer of about 15-. Also tackle these monomers Select to provide enough percentage elongations in order to the acrylic copolymer coating is stretched with rubber The exhibition or the elongation and minimum crackle is only arranged, peel off or peels off. When copolymer self adheres to the rubber table In the time of on the face, the percentage elongation of suitable copolymer is 100-500% or is more typically about 100% To about 300%.
For rubber made in accordance with the present invention, require the strictest goods and surgery article Examination gloves and surgical glove. Because their complicated shape, they must be with industry The practice that allows is taken off from mould, and a kind of good touching that have when mould is taken off also must be able to be provided The surface of sense, this sense of touch is that people select the ability with goods of well holding sense. This side Face, good sense of touch and good release property are runed counter to.
Wearing property that the reverse side of gloves must have is good (do or wet) just stretches and slips over Skin surface and do not have the ability of excessive resistance.
Stereognosis face and stripping surface can be glassy and slick, but preferably coarse and unglazed (as caused by the mould that texture mould or polishing are arranged).This wearing property surface needs the surface of natural (Course) or irregular (unglazed) more usually.
With regard to the manufacturing of gloves, multipolymer of the present invention provides good release property and/or wearing property.
According to the present invention, except the low surface energy monomer, can use following monomer and composition thereof to obtain to have good the wearing property and/or the suitable polymers of release property.
The monomer that one class is used to form multipolymer is an alkyl acrylate monomer, its moieties contains 1 to about 10 carbon atoms, forming the monomeric weight of acrylic copolymer, total amount of alkyl acrylate monomer is about 30% to about 85%, is preferably about 40% to about 85%.Operable alkyl acrylate monomer comprises methyl acrylate, ethyl propenoate, butyl acrylate, propyl acrylate, 2-EHA, Isooctyl acrylate monomer, isodecyl acrylate etc.At present preferred alkyl acrylate monomer is butyl acrylate and methyl acrylate.
Remaining monomer system is made up of hard monomer." hard monomer " used herein is in case be meant by homopolymerization then can have monomer greater than about 25 ℃ second-order transition temperature (Tg).To form the monomeric weight of acrylic copolymer, the content of hard monomer is about 20% to about 60%.
That can mention in this class monomer has a styrene monomer, as vinylbenzene, alpha-methyl styrene etc.; Alkyl methacrylate is as methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate etc.; And acid amides; As n-isobutoxy Methacrylamide etc.
This class monomer can and preferably exist one or more to contain 3 unsaturated carboxylic acids to about 5 carbon atoms, as vinylformic acid, methacrylic acid, methylene-succinic acid etc.They play the effect of improvement to rubber and other surperficial cohesive strength and promotion and rubber and other surface adhesion, and in the weight of emulsion copolymers, there is concentration in it is about 1% to 6%, preferred about 2% to about 6%.
Ground copolymerization of other and principal monomer aggressiveness of the present invention and the unsaturated vinyl monomer that does not produce the residual monomer pollution problem also can be used to improve polymer performance.
This class monomer comprises that one or more sour moieties contain 2 vinyl ester to about 16 carbon atoms.Representational vinyl ester comprises vinyl acetate, vinyl butyrate, propionate, isopropylformic acid vinyl acetate, valeric acid vinyl acetate, tertiary monocarboxylic acid (Versitate) vinyl acetate etc.
Other useful monomers that can mention has diester of dicarboxylic acid and composition thereof, and wherein the ester group of every kind of diester contains independently and has an appointment 8 to about 16 carbon atoms, and preferred about 8 to about 12 carbon atoms.Preferred diester is two-2-ethylhexyl maleic acid ester (dioctyl maleate), two-2-ethylhexyl fumarate and composition thereof.
According to the present invention, can by make above-mentioned monomer polymerization with produce a kind of have about more than 15 ℃, preferred about 15 ℃ to about 60 ℃ suitable average (or clean) second-order transition temperature (Tg) values, and the solids content scope is that about 40% of emulsion weight is made emulsion copolymers to about 70% polymkeric substance.Preferably the amount of catalyzer is that per 100 weight parts monomers about 0.15 are to about 0.5 weight part, these catalyzer such as Potassium Persulphate, tert-butyl hydroperoxide etc., and redox catalyst such as Sodium Pyrosulfite etc., in monomer weight, the content range of tensio-active agent is about 0.5% to about 5%.Temperature of reaction generally about 65 ℃ to about 85 ℃ scope.
Can comprise " chain-transfer agent ", refer to the organic compound that contains one or more thiol groups, chlorination group, hydroxyl etc., as known in the field those.At present preferred chain-transfer agent is n-dodecyl mercaptan and uncle's lauryl mercaptan, provides with the concentration that accounts for monomer weight about 0.01% to about 0.1%.In addition, by using polyfunctional acrylate and methacrylic ester can cause internal crosslinking.
Although multipolymer manufactured according to the present invention can be used for comprising that primary focus is its purposes at the manufacture view of no powder gloves and other goods in the various rubber items application of gloves, catheter, gum rubber tubing, sheath, condom etc.
Refer again to Fig. 1, apply the curved surface shaped glove mould with the acrylic copolymer that shows good release property of the present invention.Copolymer coatedly preferably apply from being mixed with to solidify the electrolytical suspension.The step that multipolymer is coated on the mould that is used for transferring to latex rubbers has replaced the step that the lime carbonate slurry is deposited to die surface, simultaneously, multipolymer deposited to have replaced with starch slurry on the molded article applies this goods.Multipolymer applies from suspension.Goods form by depositing on fixing salt such as the nitrocalcite, described fixing salt is arranged on the mould, be arranged on that copolymer coated on the mould goes up or with the multipolymer codeposition.For gloves, the mould that scribbles multipolymer with fixing salt surface (best and multipolymer codeposition) is dipped in the rubber latex, this latex coagulation is to the die surface of giving the rubber item shape, dry, sulfuration, immerse then in second kind of suspension, this second kind of suspension can be identical or another kind shows the acrylic copolymer of wearing property of excellence (promptly slip over skin surface and have the ability of minimum frictional force and obstruction).As prior art, before sulfuration or sulfuration back or before wearing property of formation coating, adopt leaching.Then the goods that form are taken off from mould.Cleaning die and recirculation.The demoulding is turned up gloves inside, thereby makes wearing property surface be positioned at gloves inside and release surface is positioned at the gloves outside.
For the manufacturing of gloves, the coarse mould of preferred at present use, as forming by producing coarse surface with sand or granulated glass sphere sandblast, through measuring, this surperficial roughness is to paddy 8-10 micron approximately by the peak.Also can adopt other structure.
Emulsion copolymers of the present invention can use like this or be used in combination with inertia granular solids such as lime carbonate, starch etc. in order to wearing property of enhancing.In total weight of solids, the inert solid content range is about 3% to about 10%.At present preferably every weight part multipolymer uses about 0.3 to about 0.7 weight part, more preferably from about 0.3 W-Gum to about 0.5 weight part, suitable W-Gum are by Roquetle America.Inc., Keokuk, the 400L-NF W-Gum that Iowa. makes.This wearing property coating preferably also contains on a small quantity (account for multipolymer weight 0.1%) oil, as different octyl pelargonate or Neobee M-20, Neobee M-20 is by Stepan Chemical Co., Northfield, a kind of polyvalent alcohol diester of lacking purification of fatty acids that Illinois makes.
Found that for good wearing property and release property every kind copolymer coated preferably by at least two kinds of polymer formation.A kind of is the multipolymer with lower glass transition temperatures, and another kind is the multipolymer with high glass-transition temperature.Two kinds of multipolymers of this that combines have produced a kind of remarkable second-order transition temperature and have been at least about 15 ℃ or more preferably at about 15 ℃ of sticking multipolymers to about 60 ℃ scope.
Although this point can be realized by using mixture of polymers, but realize by at least two kinds of monomer system sequential polymerization or " nuclear-shell " polymerization that preferably first monomer system forms second-order transition temperature and is lower than about 25 ℃, is generally approximately-50 ℃ to about 25 ℃ acrylic copolymer; Another monomer system form second-order transition temperature be about 25 ℃ to about 100 ℃ acrylic copolymer, first and second monomer system has formed sticking copolymer coated system.For the multipolymer that shows good release property, its multipolymer that is lower than 0 ℃ second-order transition temperature constitutes the major part of total glass transition temperature as can be seen.Opposite situation can be suitable for wearing property multipolymer.
Say that at length Fig. 2 is the second-order transition temperature curve of the copolymer mixture of sequential polymerization, the main second-order transition temperature peak of this copolymer mixture is lower than 0 ℃, and inferior second-order transition temperature peak height is used for as the demoulding copolymer coated in 0 ℃.Although theory of no use retrains aspect " nuclear-shell " method of using two kinds of monomer system sequential polymerization, but still think that this method of employing has formed a kind of external phase of lower glass transition temperatures multipolymer, the high glass-transition temperature multipolymer is scattered here and there in this multipolymer or on this multipolymer.
Fig. 3 has the well second-order transition temperature curve of the copolymer coating of wearing property, and wherein the intensity at corresponding second-order transition temperature peak is opposite.
In order to obtain good release property, the part by weight scope of preferably soft at present (or lower glass transition temperatures) multipolymer and high glass-transition temperature multipolymer is about 1: 1 to about 1: 3, preferably is about 1: 1.5.
In order to obtain good wearing property, the part by weight scope of lower glass transition temperatures multipolymer and high glass-transition temperature multipolymer is about 3: 1 to about 1: 1, preferably is about 1.2: 1.
As can be seen, if there is the too high multipolymer of Tg, then can peel off.In addition, for obtaining good dried wearing property, it is desirable to multipolymer and form zone or particulate.This point provides the well required uneven surface of wearing property in fact, and can comprise filler such as calcium chloride in the suspension.If use the low excessively multipolymer of second-order transition temperature, then can occur being clamminess or adhesion problems.
As discussed above, for the multipolymer manufacture method, it is desirable to adopt surfactant system, there are about 3 weight parts in its amount for having about 0.5 to about 5 weight parts in per 100 weight parts monomers, being preferably in per 100 weight parts monomers.It is desirable to equally, the suspension that is formed by emulsion copolymers allows to exist the common electrolyte that makes latex coagulation, and so that the general concentration of latex coagulation and using, promptly concentration range is about 3% to about 10% of a suspension weight.The preferred surfactants system is the mixture of aniorfic surfactant at present.A kind of molecular formula of aniorfic surfactant is C 20H 37O 7NaS contains 20 moles of ethylene oxide, and mixes use with other aniorfic surfactant, and this other anion surfactant is poly-(ethyleneoxy group) alcoholic acid salt of sulfation Nonylphenoxy and SODIUM LAURYL ETHER SULPHATE.The preferred surfactants system has been to use the SODIUM LAURYL ETHER SULPHATE that the sulfation Nonylphenoxy of 37.4% (weight) gathers the dioctyl sodium sulphosuccinate and 40.8% (weight) of (ethyleneoxy group) alcoholic acid ammonium salt, 21.8% (weight) at present.The mixture of aniorfic surfactant makes acrylic emulsions multipolymer of the present invention can form steady suspension.
Emulsion copolymers of the present invention can be made not only provides the high adhesion strength on natural rubber and synthetic rubber surface and holding force, but also provides ability and the wearable multipolymer that stretches with rubber surface.In the time of on adhering to rubber, the elongation of multipolymer is 100-500%, is preferably 100-300%, and average friction coefficient is typically about 0.25 pound of about 0.2-for about 0.3 pound of about 0.05-.Copolymer coated thickness is about 10 to about 25 microns, preferably is about the 12-16 micron.
Monomer system contains polyfunctional monomer that carries out crosslinking reaction (as tetramethyl-propane triacrylate etc.) and the chain-transfer agent as its part, has caused the formation of internal crosslinking emulsion polymer.This point is different from outside cross-linked polymer, the functional group of internal crosslinking polymkeric substance such as carboxyl, hydroxyl and/or amino the maintenance, dissociate and can be used to promote bounding force and can be used for outside crosslinking reaction, and this crosslinking reaction is as being undertaken by being exposed in photochemistry irradiation, the electron beam irradiation and/or by outside linking agent.
Emulsion polymer can use like this, or carries out modification by adding vinyl addition siloxane polymer, in the weight of emulsion polymer and vinyl addition siloxane systems, and the amount of vinyl addition siloxane polymer maximum about 30%.Used vinyl addition siloxane systems is those of siloxanyl monomers that contain band vinyl unsaturated body, when these monomers mix with the linking agent that contains silane, solidifies by group VIII metal catalyst (preferred platinum catalysts).
At present preferred vinyl addition silicone emulsion is the reaction-ity ethylene radical siloxane polymkeric substance of following formula
Figure C9619282200161
The silane crosslinker mixture of polymers of (wherein m and n are independently integer) and following formula:
Figure C9619282200171
(wherein m and p are independent integers).
Also can comprise the conventional composition that is used to improve release property.
Vinyl addition siloxane systems reacts by the addition-curing (hydrosilication) between thermal initiation polydimethyl-hydrogen siloxane linking agent and the reaction-ity ethylene base functional siloxane polymkeric substance, so that cured polymer to be provided.
The siloxane polymer of vinyl functional is a polydimethylsiloxane, and wherein a part of methyl is replaced by vinyl or the group that contains the unsaturated body of vinyl, i.e. reaction occurs between the polydimethylsiloxane and polydimethyl hydrogen siloxane of vinyl substituted.
Whole hydrosilation reaction is catalytic by the coordination compound of the group VIII transition metal that dissolves in siloxanes (especially platinum).In the routine of ethene addition siloxane systems is used, before depositing on the ground, add a small amount of inhibitor and mix the premature reaction between back silane and the vinylsiloxane group to prevent coating composition.During hot sulfurization, its inefficacy is removed or made to this inhibitor.Being suitable for implementing silicone emulsion system of the present invention can obtain from Dow Corning, Rhone-Poulenc and Wacker-Chemic GmbH, for example Wacker VP 1571E/1572 system.
During letex polymerization, with regard to the efficient of emulsion polymerization process, emulsion copolymers of the present invention forms high solids content.For on the mould of the rubber item that is used to be coated to moulding soon or be coated in type rubber item, usually the emulsion copolymers dilution had suspension than low solid content with formation.As known in the field, the typical solid content range is about 3% to about 10% of a suspension weight.
Need peptizer salt from its emulsion (latex), to deposit on the surface of polymkeric substance to cause rubber.Can after the multipolymer drying on the die surface, apply peptizer, mix and the remarkable saving of realization time and cost with copolymer soliquoid by making peptizer.In a single day be surprised to find that multicomponent aniorfic surfactant system of having used, copolymer soliquoid of the present invention just allows to exist the polyvalent metal salt that measures the peptizer effect greatly.The example of adoptable peptizer is the water-soluble salt of calcium, zinc, aluminium etc.Nitrocalcite preferably at present.Peptizer salt (preferred nitrocalcite) generally accounts for about 20% to about 40% concentration with about at the most 40%, the typical case who accounts for the suspension weight that applies mould and provides.Peptizer is combined an important step of having saved in the rubber item process for preparing the multipolymer coating with emulsion polymer of the present invention.If debond peptizer and apply multipolymer must be deposited on the die surface and after the drying peptizer is coated in this multipolymer surface thereon so at multipolymer.This has just increased a step, and has therefore increased cost.
At present preferred mould be the band texture or slick ceramic, porcelain or have the smooth surface mould on fluorocarbon surface, this mould allows multipolymer or multipolymer and peptizer to apply thereon, and allows the rubber item demoulding of moulding when production process finishes.
Be immersed in time length in the rubber latex and determined the thickness of the rubber coating that forms.Typical thickness is about 6 to about 10 mils.
After shifting out rubber latex, can make the rubber item seasoning of solidifying or heat drying in baking oven.Then with the leaching in water of moulding rubber item.Make the filterable rubber coating sulfuration of drop then.
After the sulfuration, make the multipolymer that is coated with rubber be cooled to about 60-80 ℃, immerse then in second kind of acrylic emulsions copolymer soliquoid, preferably do not contain peptizer in this suspension, need another step leaching to avoid producing the salt refuse.The immersion time is about 3 to about 6 seconds.Coating is following dry about 2-3 minute at about 100-125 ℃.
Then the goods of dual coating are cooled to about 40 ℃ and take off from mould.Because knockout course routs up gloves inside, thereby second coating becomes the wearing property coating with tissue or skin contact, simultaneously, becomes touch coatings as outside (or outside) coating of release coating.
Be used for the copolymer coated of rubber item (especially gloves) although the focus of above-mentioned discussion is meant, found that this multipolymer has other purposes, especially the coating of using as automotive industry that is called " soft sense of touch " product.Such example provides the polymeric layer stampings that have the leather outward appearance and have corresponding feel.
But successfully measured the laminated product that multipolymer of the present invention can be used for vacuum forming.The structure of these goods should be made of the polyester film as carrier, and this polyester film was removed before vacuum forming.Multipolymer of the present invention is deposited on the carrier with as transparent or painted finishing coat with about 0.25 thickness to about 2 mils, and as the surface that is touched by the user.Deposit remaining composition material so that outward appearances such as leather, wood grain to be provided, increase or guaranteed " soft sense of touch " with the form of copolymer layer of the present invention.Add one deck heat-activatable adhesive then, heat pressure adhesive subsequently is to produce the polymeric material sheet of 20 mil thick compatible with injection-moulded plastic.Remove polyester support then, with the laminated product vacuum forming and carry out embedding mould has uniqueness and ideal soft feel(ing) with generation curved surface parts of plastics.
Multipolymer of the present invention also can or be deposited on back side opposite side as sprayed coating and have on the lining of pressure sensitive adhesive.This multipolymer provides protectiveness and uncommon " soft sense of touch " use properties.In these two kinds of application, think that this polymkeric substance is owing to containing siloxanes and acrylic monomer thereby having uncommon external performance.
Embodiment 1-is used for the emulsion copolymers of the demoulding
With parts by weight is that benchmark is made following two kinds of soap lye.First soap lye contains 98.2 parts by weight of deionized water, 0.87 weight part tetrasodium pyrophosphate, 10.9 weight part Aerosol TMNPES 458 (58% solution of poly-(inferior ethoxyl) alcoholic acid ammonium salt of a kind of sulfation nonyl is made by Cyanamid), 4.9 weight part Aerosol TMOT75 (a kind of 75% solution of dioctyl sodium sulfonate) and 3 weight part Disponil FE S77 (a kind of 32.5% solution of Zetesol NL, make by Henkel), second soap lye contains 82.2 parts of deionized waters, 0.73 part of tetrasodium pyrophosphate, 450,4.1 parts of OT75 of 9.1 parts of NPES and 17.8 parts of FES77 tensio-active agents.
Make two independently monomer systems.First monomer system contains 39.6 parts of vinylbenzene, 318 parts of butyl acrylates, 50 parts of methyl acrylates, 3.8 parts of methacrylic acids, 3.8 parts of vinylformic acid, 71.3 parts of RC726 (a kind of siloxanes acrylate is made and sold by Goldschmidt), 30 parts of GE siloxanes SL 6000-D1 and 23.5 parts of GE siloxanes SL6010-D1.
Second monomer system contains 210 parts of vinylbenzene, 102.9 parts of butyl acrylates, 43.9 parts of methyl acrylates, 3 parts of methacrylic acids, 2.7 parts of vinylformic acid and 56 parts of GE siloxanes SL6000-D1.
Make the catalyst solution that contains 78 parts of deionized waters and 2 parts of Potassium Persulphates respectively, and the activator solution that contains 78.5 parts of deionized waters and 1.5 parts of sodium metabisulfites.Make the initial admixture of reactor that contains 320 parts of deionized waters, 458,4.5 parts of sodium bicarbonates of 0.08 part of NPES and 3.85 parts of Potassium Persulphates and 0.15 part of sodium metabisulfite.Under agitation in the initial admixture of this reactor, add the mixture of first monomer in first soap lye lentamente, further add activator solution subsequently, further add catalyzer then.Temperature of reactor remains between 65-73 ℃.After reaction is finished, further add and contain second batch of monomeric second soap lye.After reaction is finished, handle with the aqueous solution of ammonium and biocides.The pH value of gained emulsion is 8.7, and solids content is 57%.Embodiment 2-is used for the dried emulsion copolymers that wears
Basically be the step of repetition embodiment 1, different is that each components in proportions is 95 parts of vinylbenzene, 220.7 parts of butyl acrylates, 38.8 parts of methyl acrylates, 9.8 parts of vinylformic acid, 15 parts of GE SL 6000-D1,9 parts of TMPTAs and 3.3 parts of n-isobutoxy Methacrylamides in first monomer.
For the second endorsement body, what adopt is the monomer mixture of 302.3 parts of vinylbenzene, 146.2 parts of butyl acrylates, 57.9 parts of methyl acrylates, 17.5 parts of vinylformic acid, 40.4 parts of GE SL 6000-D1,20 parts of TMPTAs and 4.48 parts of N-isobutoxy Methacrylamides, and further the catalyst solution that adds contains 70.5 parts of deionized waters and 2.5 parts of Potassium Persulphates.First soap lye and first monomer that will contain 458,3.3 parts of OT75 of 6.91 parts of NPES and 14.7 parts of FES77 add in the initial admixture of reactor, further add catalyst solution subsequently, after reaction is finished, further add second monomer of mixing in the soap lye that contains 4.9 parts of OT75,10.29 parts of NPES458 and 21.89 parts of FES77.Temperature is remained on 78-85 ℃, and after ammonium biocides solution-treated, the pH value of emulsion is 6.6, and total solids level is 57.6%.
Embodiment 3-makes gloves
Be coated on the mould of examination gloves with the multipolymer of embodiment 1 with as the nitrocalcite of peptizer.The mould that applies is immersed in the latex solution, and rest in this solution up to the rubber coating that on coating, forms the 6-10 mil.Then this rubber coating is immersed in the solids suspension of multipolymer of embodiment 2.After the coating drying of the multipolymer of embodiment 2, gloves are taken off from mould.
Formed gloves do not have white point, and with the after fixing coating of embodiment 1 multipolymer as the glossiness outside, with the coating of embodiment 2 multipolymers as unglazed side.Embodiment 1 and 2 multipolymer stick on the latex securely and formed has the excellent gloves as latex examination gloves of doing wet wearing property.Do not peel off when stretching these gloves.Shown in Figure 3 is main second-order transition temperature peak-21.04 ℃ ,-11.74 ℃ ,+12.45 ℃ and+the DSC distribution plan of 28.55 ℃ multipolymer.Configuration of surface shows as the slight irregular continuous surface that has little hole and submicron projection, and the diameter in this little hole is 0.1 to 1 μ m.Shown in Figure 4 is DSC graphic representation and several second-order transition temperatures peak of this polymkeric substance, and main several peaks are at-12.51 ℃, 13.57 ℃ and 29.76 ℃.Form show as have the submicron projection, the slight irregular surface in submicron shallow hole and accumulative particulate state projection and little hole.Embodiment 4-is used for the dried emulsion copolymers that wears
Making a kind of surfactant soln, is benchmark with parts by weight, contains 122.70 parts of deionized waters, 1.60 parts of tetrasodium pyrophosphate (0.96 part of dry-matter), 31.27 parts of tensio-active agents (21.56 parts of dry-matteies).
Make a kind of monomer mixture independently, with parts by weight is benchmark, contain 100 parts of vinylbenzene, 405.12 parts of butyl acrylates, 37.42 parts of methyl acrylates, 6.5 parts of methacrylic acids, 12.30 parts of vinylformic acid, 6.25 parts of RC705 (a kind of siloxanes acrylate is sold by Goldschmidt) and 0.08 part of n-dodecane mercaptan.By the part by weight of 4 parts of monomers monomer mixture is added in the surfactant soln than 1 part of surfactant soln.
Make a kind of catalyst solution of further adding independently, this solution is made up of 63 parts by weight of deionized water and 2 weight part Potassium Persulphates and low quantity of surfactant.
In a reactor stirring, that nitrogen covers, after adding 200 parts by weight of deionized water, 3.08 weight part tensio-active agents and 1.5 parts of Potassium Persulphates, so that reaction follows the speed of slight temperature rise further to add monomer and surfactant soln and catalyst solution when carrying out.Temperature is remained on 80 ± 2 ℃.Form a kind of total solids level and be about 54.3% emulsion.With biocides/ammonium neutralizer this emulsion is adjusted to the pH value and is about 6.5.Embodiment 5-is used for the dried emulsion copolymers that wears
Basically repeat embodiment 4, different is, with parts by weight is benchmark, monomer mixture contains 219.2 parts of methyl methacrylates, 219.2 parts of butyl acrylates, 51.33 parts of methacrylic acids, 13 parts of n-isobutyl-methacrylic esters, 16.66 parts of siloxanes acrylate (RC705) and 0.13 part of n-dodecane mercaptan, and surfactant soln is made up of 27.73 parts of Aerosol NPES930,2.7 parts of OT75 and 24.9 parts of FES-77 and 0.66 part of sodium metabisulfite and 18.81 parts of tensio-active agents of being dissolved in 113.3 parts of deionized waters.
Embodiment 6-makes gloves
As calculated, with the emulsion copolymers of embodiment 5 be 4.8% suspension as a kind of solid content that contains 4.5% soap.Apply a kind of clean examination gloves with this suspension.The deposited coatings of gained provides extraordinary dried wearing property and detachability.Do not peel off.The manufacturing of dried wearing property multipolymer of embodiment 7-and gloves
After the step of embodiment 4, formed a kind of multipolymer that contains 46.4% (weight) vinylbenzene, 38% (weight) butyl acrylate, 1.3% (weight) methacrylic acid, 3.3% (weight) vinylformic acid, 8.5% (weight) siloxanes acrylate and 1.9% (weight) isobutoxy Methacrylamide.Formed multipolymer is combined with the vegetables oil that accounts for multipolymer weight 0.6%, have the well multipolymer of wearing property for the manufacturing gloves provide.The manufacturing of dried wearing property multipolymer of embodiment 8-and gloves
Make a kind of mixture of multipolymer, the part by weight of the multipolymer of embodiment 5 and a kind of multipolymer that is obtained by 48.2% (weight) vinylbenzene, 33.1% (weight) butyl acrylate, 6.1% (weight) methyl acrylate, 1.1% (weight) methacrylic acid, 2.1% (weight) vinylformic acid, 6.3% (weight) siloxanes acrylate, 0.9% (weight) n-isobutoxy Methacrylamide and the letex polymerization of 2.3% (weight) TMPTA is 1: 3 in this mixture.This mixture of polymers is deposited on the mould.Peptizer is a nitrocalcite.Adopt the method for embodiment 3 on this multipolymer, to form the latex coating.The manufacturing of dried wearing property multipolymer of embodiment 9-and gloves
Make a kind of emulsion copolymers by the monomer mixture that contains 43% (weight) vinylbenzene, 36.5% (weight) butyl acrylate, 8.6% (weight) methyl acrylate, 1% (weight) methacrylic acid, 1.9% (weight) vinylformic acid, 5.2% (weight) siloxanes acrylate, 0.8% (weight) n-isobutoxy Methacrylamide and 3% (weight) TMPTA.The suspension of this multipolymer is coated on medium size and the large size glove mould, adopts the step of embodiment 3 to make copolymer coated going up form rubber coating.
Embodiment 10-measures frictional force
In order to measure copolymer coated skin friction force, prepare 1 inch wide sample, with 200g slide plate of the pinblock speed of 15 inch per minute clocks pulling, it is 5/8 inch that this slide plate has three diameters, be positioned at the granulated glass sphere at the place, angle of equilateral triangle on this sample.The required resistance of pulling slide plate is about 0.112 pound on powder surface.Chlorinated surface and biogel surface need 0.07 ft lbf.By contrast, undressed surface provides about 0.33 and 0.34 pound resistance, has the trend that slide plate is risen from its residing surface, and has not steady significantly mobile trend.The composition of embodiment 7 needs about 0.22 pound power.The polymeric blends of embodiment 8 needs about 0.23 pound power, the composition of embodiment 9 is when depositing from the suspension of 6% solids content when it, need about 0.22 pound power, when it is when depositing from the suspension of 8% solids content, resistance increases to about 0.225 pound.Measurement is to carry out under the temperature of 50% humidity and 23 ℃.Embodiment 11-is used for the emulsion copolymers of supercoat
Basically repeat the step of embodiment 1, different is that each components in proportions is 150 parts of vinylbenzene, 237 parts of butyl acrylates, 22 parts of vinylformic acid, 31 parts of RC726,9 parts of methacrylic acid triacrylates and 8.7 parts of N-isobutoxy Methacrylamides in first monomer.
For the second endorsement body, what adopt is the monomer mixture of 348 parts of vinylbenzene, 136.6 parts of butyl acrylates, 9 parts of methacrylic acids, 248 parts of vinylformic acid, 30.8 parts of RC726,8.7 parts of N-isobutoxy Methacrylamides, and further the catalyst solution that adds contains 70.5 parts of deionized waters and 2.5 parts of Potassium Persulphates.Forming total solids level by the order letex polymerization is 53.3 copolymer emulsion.Formed multipolymer provides the aggressiveness supercoat for rubber surface.
Wearing property of embodiment 12-coating
The aqueous solution of the copolymer emulsion of embodiment 1 is combined with the lime carbonate that amount accounts for this emulsion weight about 3.3%, added water and minor amounts of propylene glycol dicaprylate when forming the above-mentioned aqueous solution.This mixture has produced a kind of excellent combination thing that wet and dried wearing property surface are provided for gloves.
Embodiment 13
Repeat embodiment 12, different is to replace lime carbonate with starch.Coating still has excellent doing and wet wearing property.

Claims (29)

1 one kinds of compositions that on product surface, form polymeric coating, said composition comprises a kind of not waterborne suspension of sticking acrylic emulsions multipolymer, this multipolymer is made of the reaction product of following material: 0.7-20% (weight) but at least a copolymerization low surface energy monomer, but but should copolymerization low surface energy monomer be a kind of siloxane oligomer of copolymerization, at least a its moieties of 30-85% (weight) has the alkyl acrylate of 1-10 carbon atom, all the other monomers comprise hard monomer, described hard monomer has the second-order transition temperature more than 25 ℃ when homopolymerization, and its amount is enough to form described not sticking acrylic emulsions multipolymer.
2. the composition of claim 1, but wherein the monomeric amount of copolymerization low surface energy accounts for the 1-15% of acrylic copolymer weight.
3. claim 1 or 2 composition, wherein alkyl acrylate is selected from methyl acrylate, butyl acrylate and composition thereof.
4. claim 1 or 2 composition, wherein hard monomer comprises the monomer of the unsaturated carboxylic acid, acid amides and their mixture that are selected from styrene monomer, alkyl methacrylate, have 3-5 carbon atom.
5. claim 1 or 2 composition, said composition comprises a kind of not waterborne suspension of sticking acrylic emulsions multipolymer, this multipolymer contain 0.7-20% (weight) but the siloxane oligomer of at least a copolymerization, the alkyl acrylate that is selected from methyl acrylate, butyl acrylate and composition thereof of 40-80% (weight), remaining monomer are selected from vinylbenzene, methacrylic acid, vinylformic acid, methyl methacrylate, isobutoxy Methacrylamide, Propenoic acid, 2-methyl, isobutyl ester and their mixture.
6. claim 1 or 2 composition, wherein suspension contains at least two kinds of anion surfactants.
7. the composition of claim 6, wherein anion surfactant is selected from dioctyl sulfo-sodium succinate, poly-(inferior ethoxyl) the alcoholic acid ammonium salt of sulfonation Nonylphenoxy and fatty alcohol polyglycol ether sulfuric ester.
8. aforementioned claim 1 or 2 composition, said composition comprises the emulsion copolymers mixture of being made up of the first acrylic emulsions multipolymer and the second acrylic emulsions multipolymer, described first and second multipolymers form by following monomeric letex polymerization: 0.7-20% (weight) but the siloxane oligomer of at least a copolymerization, its moieties of 30-85% (weight) has at least a alkyl acrylate of 1-10 carbon atom, all the other monomers comprise hard monomer, this hard monomer has the second-order transition temperature more than 25 ℃ when homopolymerization, and provide to be enough to form a kind of not amount of first and second sticking acrylic emulsions copolymer mixture, the second-order transition temperature of the described first acrylic emulsions multipolymer is-50 ℃ to 25 ℃, and the second-order transition temperature of the described second acrylic emulsions multipolymer is 25 ℃ to 100 ℃.
9. the composition of claim 8, wherein the part by weight scope of the first acrylic emulsions multipolymer and the second acrylic emulsions multipolymer is 1: 1 to 1: 3.
10. the composition of claim 8, wherein the part by weight of the first acrylic emulsions multipolymer and second multipolymer is 1: 1.5.
11. the polymer composition of claim 8, wherein the part by weight scope of the first acrylic emulsions multipolymer and second acrylic copolymer is 3: 1 to 1: 1.
12. the composition of claim 8, wherein the part by weight of the first acrylic emulsions multipolymer and the second acrylic emulsions multipolymer is 1.2: 1.
13. the composition of claim 1 or 2, said composition comprises the first acrylic emulsions multipolymer and the second acrylic emulsions multipolymer, the first acrylic emulsions multipolymer is to comprise vinylbenzene, butyl acrylate, methyl acrylate, methacrylic acid, but vinylformic acid and at least a copolymerized siloxanes oligopolymer are in the reaction product of the first interior monomer system, the second-order transition temperature of this first emulsion copolymers is less than 0 ℃, the second acrylic emulsions multipolymer is second monomer system carries out sequential polymerization in the presence of first emulsion copolymers a reaction product, described second monomer system is by vinylbenzene, butyl acrylate, methyl acrylate, methacrylic acid, but vinylformic acid and at least a copolymerized siloxanes oligopolymer are formed, the second-order transition temperature of described second multipolymer is 0-100 ℃, the sequential polymerization mixture of the described first and second acrylic emulsions multipolymers cannot not be sticking, and forms in the presence of at least two kinds of anion surfactants.
14. being used to prepare, each described composition of claim 1-13 deposited the purposes of goods of coating that one deck derives from the waterborne suspension of at least a emulsion copolymers on a kind of its surface, described emulsion copolymers is made up of following material: 0.7-20% (weight) but at least a copolymerization low surface energy monomer, at least a its moieties of 30-85% (weight) has the alkyl acrylate of 1-10 carbon atom, remaining monomer comprises hard monomer, described hard monomer has the second-order transition temperature more than 25 ℃ when homopolymerization, and its amount is enough to form a kind of not sticking acrylic emulsions multipolymer.
15. each described composition of claim 1-13 is used to prepare and has deposited one deck on a kind of its surface and derive from and contain the purposes of the goods of the coating of the waterborne suspension of sticking acrylic emulsions multipolymer of resilient no powder, described acrylic emulsions multipolymer is made up of following material: 0.7-20% (weight) but at least a copolymerization low surface energy monomer, this monomer is a siloxane oligomer, at least a its moieties of 30-85% (weight) has the alkyl acrylate of 1-10 carbon atom, remaining monomer comprises hard monomer, described hard monomer has the second-order transition temperature more than 25 ℃ when homopolymerization, and its amount is enough to form a kind of sticking acrylic emulsions multipolymer, and described goods are rubber items.
16. each described composition of claim 1-13 is used for preparing a kind of by rubber being solidified to the purposes of the goods that form on the mould from latex, have the no powder of forming by the acrylic emulsions multipolymer on its at least one surface, Nian adhesion is flexible not polymer coated, described acrylic emulsions multipolymer is to obtain from the monomer system letex polymerization of being made up of following material: add up to 0.7-20% (weight) but at least a copolymerization low surface energy monomer, this monomer is a siloxane oligomer, at least a alkyl acrylate of 30-85% (weight), be selected from methyl acrylate, ethyl propenoate, butyl acrylate and composition thereof, all the other monomers are made up of hard monomer, this hard monomer has the second-order transition temperature more than 25 ℃ when homopolymerization, and to be enough to form not the amount of slimy milk liquid multipolymer provides, described emulsion copolymers is sedimentary from the waterborne suspension of emulsion copolymers.
17. each purposes among the claim 14-16, but wherein the monomeric amount of copolymerization low surface energy accounts for about 1-15% of acrylic copolymer weight.
18. each purposes among the claim 14-16, wherein alkyl acrylate is selected from methyl acrylate, butyl acrylate and composition thereof.
19. each purposes among the claim 14-16, wherein hard monomer comprises the monomer of the unsaturated carboxylic acid, acid amides and their mixture that are selected from styrene monomer, alkyl methacrylate, have 3-5 carbon atom.
20. each purposes among the claim 14-16, these goods are gloves shapes, and form by solidify rubber from latex.
21. each purposes among the claim 14-16, wherein multipolymer contains the compound granular solids that is selected from lime carbonate and starch, and this multipolymer is deposited on the moulded products or is deposited on the mould that forms these goods.
22. the purposes of claim 20, the goods of wherein making are the rubber glovess with internal surface and outside surface, have one deck on the described internal surface by the coating that wears that the first acrylic emulsions multipolymer forms, have the release coating that one deck is formed by the second acrylic emulsions multipolymer on the described outside surface.
23. the purposes of claim 22, wherein first and second coatings are identical.
24. the purposes of claim 22, wherein first and second coatings are different.
25. the purposes of claim 16, wherein polymer coatedly comprise a kind of adherent acrylic emulsions multipolymer, this multipolymer is to form from the monomer of being made up of following material: 0.7-20% (weight) but the copolymerized siloxanes oligopolymer, at least a methyl acrylate that is selected from of 40-80% (weight), the alkyl acrylate of butyl acrylate and composition thereof, and at least a vinylbenzene that is selected from, methacrylic acid, vinylformic acid, methyl methacrylate, the isobutoxy Methacrylamide, the monomer of Propenoic acid, 2-methyl, isobutyl ester and their mixture, described emulsion copolymers are sedimentary from the waterborne suspension of emulsion copolymers.
26. the purposes of claim 16, its floating coat comprises the first acrylic emulsions multipolymer and the second acrylic emulsions multipolymer, described first and second multipolymers are to form by the monomeric letex polymerization that following material is formed: 0.7-20% (weight) but at least a copolymerized siloxanes oligopolymer, at least a its moieties of 30-85% (weight) has the alkyl acrylate of 1-10 carbon atom, all the other monomers comprise hard monomer, this monomer has the second-order transition temperature more than 0 ℃ when homopolymerization, and provide to be enough to form a kind of not amount of sticking acrylic emulsions copolymer mixture, the main second-order transition temperature peak of the described first acrylic emulsions multipolymer is between-50 ℃ to 25 ℃, and the main second-order transition temperature peak of the described second acrylic emulsions multipolymer is between 25 ℃ to 100 ℃.
27. the purposes of claim 26, wherein the part by weight scope of the first acrylic emulsions multipolymer and the second acrylic emulsions multipolymer is 1: 1 to 1: 3.
28. the purposes of claim 26, wherein the part by weight scope of the first acrylic emulsions multipolymer and second acrylic copolymer is 3: 1 to 1: 1.
29. the purposes of claim 26, wherein mixture comprises the first not sticking acrylic emulsions multipolymer and the second acrylic emulsions multipolymer, the first not sticking acrylic emulsions multipolymer comprises the reaction product of first monomer system, this first monomer system contains vinylbenzene, butyl acrylate, methyl acrylate, methacrylic acid, but the siloxane oligomer of vinylformic acid and at least a copolymerization, the second acrylic emulsions multipolymer is second monomer system carries out sequential polymerization in the presence of first emulsion copolymers a reaction product, described second monomer system is by vinylbenzene, butyl acrylate, methyl acrylate, methacrylic acid, but the siloxane oligomer of vinylformic acid and at least a copolymerization is formed, the sequential polymerization mixture of the described first and second acrylic emulsions multipolymers cannot not be sticking, and forms in the presence of at least two kinds of anion surfactants.
CN96192822A 1995-02-14 1996-02-12 Acrylic emulsion coatings for rubber articles Expired - Fee Related CN1078123C (en)

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US38957195A 1995-02-14 1995-02-14
US08/388,030 US5691069A (en) 1995-02-14 1995-02-14 Acrylic emulsion coatings for rubber articles
US08/388,030 1995-02-14
US08/389,571 1995-02-14
US48671095A 1995-06-07 1995-06-07
US08/486,948 US5712346A (en) 1995-02-14 1995-06-07 Acrylic emulsion coatings
US08/486,947 1995-06-07
US08/486,947 US5700585A (en) 1995-02-14 1995-06-07 Acrylic emulsion coatings for formed articles
US08/486,948 1995-06-07
US08/486,710 1995-06-07

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AU4977596A (en) 1996-09-04
MX9706202A (en) 1997-10-31
ID23598A (en) 1996-08-22
EP0809565A1 (en) 1997-12-03
WO1996025278A1 (en) 1996-08-22
JPH11507085A (en) 1999-06-22
IL117123A (en) 2002-04-21
IL117123A0 (en) 1996-06-18
AU710920B2 (en) 1999-09-30
CA2212861A1 (en) 1996-08-22
EP0809565A4 (en) 1998-05-06
CN1179745A (en) 1998-04-22

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