CN1061356C - Cold sealable cohesive polymers - Google Patents
Cold sealable cohesive polymers Download PDFInfo
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- CN1061356C CN1061356C CN94194368A CN94194368A CN1061356C CN 1061356 C CN1061356 C CN 1061356C CN 94194368 A CN94194368 A CN 94194368A CN 94194368 A CN94194368 A CN 94194368A CN 1061356 C CN1061356 C CN 1061356C
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- 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
- C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/54—Inorganic substances
Abstract
A copolymer preparable by the emulsion polymerisation of: a) at least one monomer which comprises an alkyl methacrylate having from 1 to 12 carbon atoms in the alkyl group; a vinyl aromatic; or a nitrile having ethylene unsaturation conjugated with the nitrile group, with at least one of the following: b) at least one copolymerisable soft monomer; and c) at least one copolymerisable functional monomer, the resulting copolymer having a glass transition temperature (Tg) from -35 DEG C to 50 DEG C and being formulatable into a coating which is cold sealable to itself under pressure but which has non-blocking characteristics.
Description
The present invention relates to the binder polymer of cold sealable; Be particularly related to multipolymer with emulsion copolymerization preparation, this multipolymer preparation, contain this multipolymer cold sealable composition, contain the cold sealed structure of this multipolymer, to the sealing of this structure with the composition coat plastics film of this cold sealable.
Can make effectively sealing of plastic wrapping structure (as plastic film) by coating adhesive.This coating can be a heat seal coating, the sealing when heating of its adhesive coatings; Maybe can be cold seal coating, they can be at 0 ℃ of-40 ℃ of lower seal.In food Package, particularly in packing, must avoid using needing heat treated device in order to avoid products to be packaged rotten to thermo-responsive food (as candy, chocolate and ice-creams).
In seal process, do not need to use cold sealing pressure sensitive coatings heater element, commercially available to have high surface viscosity in the past, be easy to adhesion.
The present invention wants to provide a kind of polymkeric substance, and its prescription can provide a kind of pressure sensitive adhesion coating of cold sealing, and is just bonding and commercially available acrylic coating had low surface viscosity, not adhesion with it when this coating only contacts with the surface of similar coating under pressure.Simultaneously coating also need (comprise plastic film and paper) and have good wettability, good coating homogeneity and good cohesive strength on various substrates.Can not lower speed simultaneously at alap temperature lower seal.At last, coating should free from extraneous odour, can be used for food, have good optical performance (as gloss).
Therefore, one aspect of the present invention provides a kind of by emulsion copolymerization, the multipolymer of aqueous phase emulsion copolymerization preferably, wherein:
A) at least a monomer, this monomer comprise alkyl methacrylate with 1-12 carbon atom alkyl group, vinylaromatic hydrocarbon or one conjugation on itrile group unsaturated ethylene linkage
Nitrile, with at least a following:
B) but the tenderizer monomer of at least a copolymerization and
C) but the monomer of at least a copolymerization.
The second-order transition temperature (Tg) of the final multipolymer that produces is-35 ℃ to 50 ℃, and its coating that is made into is the cold sealing of energy each other under pressure, but can not stick together.
Suitable monomers (a) comprising: methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, propyl group n-butyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate, methacrylic acid n-pentyl ester, methacrylic isoamyl valerate, N-Hexyl methacrylate, n octyl methacrylate, the own ester of methacrylic acid (2-ethyl), decyl-octyl methacrylate, methacrylic acid dodecane ester; Vinylbenzene, alpha-alkyl phenylethylene, Vinyl toluene; Vinyl cyanide, methacrylonitrile, specially suitable is methyl methacrylate or vinyl cyanide.
When monomer (a) comprised alkyl methacrylate or vinylaromatic hydrocarbon, its suitable consumption was 21%-55% (weight is based on the gross weight of monomer mixture, down together), is preferably 30%-45%, preferably 35%-42%.In addition when monomer (a) when also containing nitrile, the consumption of suitable nitrile can preferably not be higher than 10% (as 3%-9%) up to 25%.When monomer (a) when only containing nitrile, suitable nitrile consumption is 10%-65%.
Suitable monomers (b) comprising: the alkyl acrylate with 1-12 carbon atom alkyl group; 1,3-butadiene; Or vinyl or inclined to one side vinyl ester, preferable have methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, vinylformic acid n-pentyl ester, vinylformic acid isopentyl ester, Ethyl acrylate, vinylformic acid n-octyl, Isooctyl acrylate monomer, the own ester of vinylformic acid (2-ethyl), a decyl acrylate, 1,3-divinyl, vinyl-acetic ester or vinylidene chloride, best is methyl acrylate or ethyl propenoate.
Suitable monomers (b) is preferably 40%-69% for consumption is 30%-85%, is preferably 48%-60%.
Suitable monomers (c) comprises the ethylene linkage unsaturated compound that contains carboxylic acid or sulfonic acid group, and requirement is α, β-ethylene linkage unsaturated carboxylic acid, preferably vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, toxilic acid or methacrylic acid sulfonation ethyl ester.Specially suitable is acrylic or methacrylic acid.
The consumption of suitable monomers (c) is 1%-15% (as 1%-5%), is preferably 2%-8%.
One aspect of the present invention requires the T of multipolymer
gValue is for-30 ℃ to 15 ℃.And requiring this multipolymer to comprise the comonomer (a) of 10%-65% (weight), the comonomer (b) of 30%-85% (weight) and the comonomer (c) of 1%-5% (weight), the number average molecular weight of this multipolymer reaches 150,000 (GPC).Preferably the number average molecular weight of this multipolymer is 50,000-90,000.
The present invention requires the T of multipolymer on the other hand
gValue is 25 ℃ to 50 ℃, is preferably 30 ℃ to 50 ℃.And require this copolymerization to comprise the comonomer (a) of 30%-55% (weight), the comonomer (b) of 40%-69% (weight) and the polymer monomers (c) of 1%-15% (weight).The number average molecular weight of this multipolymer is 8, and 000-12 is between 000 (GPC, with respect to polystyrene standard and be dissolved in the tetrahydrofuran (THF)).
Generally, every kind of monomeric amount depends on the desired second-order transition temperature of multipolymer of the present invention.This available following formula is expressed:
Wherein:
T
gThe second-order transition temperature of expression multipolymer of the present invention;
W
FiThe weight percent of expression monomer (i);
T
GiThe second-order transition temperature of the homopolymer of expression monomer (i).
Following table has been listed typical T
Gi
List body (a) Tgi (℃) acrylonitrile 97 monomers (b) ethyl acrylate-22 Hexyl 2-propenoate-57 isopropyl acrylate-3 propylene different monooctyl ester-85 butyl acrylate-54 methyl acrylate 8 vinylidene chlorides-17 isobutyl acrylate-431,3-butadiene-78 vinyl acetate-32 monomer (c) acrylic acid 106 methacrylic acids 185 itaconic acids ... methacrylic acid sulfonation ethyl ester ... maleic acid ... crotonic acid
The present invention finds that multipolymer demonstrates good pressure sealing under low second-order transition temperature (typically be lower than 3 ℃, more typically be lower than 0 ℃, most typical be lower than-5 ℃), but this difference with used comonomer changes.The mean diameter of polymer particles is the 0.05-0.3 micron.
The acid number of typical multipolymer of the present invention is 10-100mg KOH/g.
Can require multipolymer of the present invention is carried out crosslinked, can be with a spot of linking agent (weight percent be often less than 5%), the linking agent of in technology, knowing as divinylbenzene or 1,3 butylene glycol dimethacrylate or other.
The present invention find require to be used to reduce the chain-transfer agent of average molecular weight of copolymer the effect influence that is crosslinked agent offset; So, when using a large amount of linking agents, often use a large amount of chain-transfer agents, vice versa.This helps balance cohesive strength and stopping property.
On the other hand, the present invention also provides a kind of technology for preparing multipolymer, and this technology comprises: at least a monomer (a) is mixed mutually with at least a monomer (b) with (c), make the T of the multipolymer that obtains
gValue is for-35 ℃ to 50 ℃;
(B) under the letex polymerization condition, make monomer polymerization.
The typical preparation method of multipolymer of the present invention is that (for example at a stirring reactor with heating and condensing works) makes by emulsion polymerization technique in a familiar equipment; Can adopt any monomer and relative proportion of describing herein.The existence meeting of water, emulsifying agent and catalyzer (a kind of free radical catalyst or a kind of redox system) exerts an influence to polyreaction.
The reactor feed process comprises that all monomers of adding, water, emulsion and catalyzer are to form solution.Also can add the part catalyzer earlier, remainder slowly adds in polymerization process.Also can begin to add earlier portion water, part emulsion, and remainder water and emulsion made a kind of pre-emulsion with monomer mixture, this pre-emulsion adds in the reactor under polymerization temperature at leisure, equally, catalyzer also can add or add earlier a part from the just a part ground of beginning, and remaining separately adds.Also can add monomer mixture with the form of pre-emulsion, add whole residual monomers mixtures, promptly not have water and emulsion this moment in subordinate phase in the starting stage, and individually but add catalyzer abreast.Method is to add entry and emulsifier solution earlier preferably, under polymerization temperature, in water, add monomer mixture and catalyzer then separately but abreast, at leisure, subsequently, restock adds emulsifying agent, in the second step polymerization, the residual monomers mixture is added in the reactor, and the catalyzer that does not have at first to add also can add in the reactor after adding monomer fully.But the method that this back adds catalyzer is not very good.
Preferably select the mass ratio of suitable monomer and water so that the acrylate copolymer dispersion that obtains has the solids content of 20-40%.
Typical catalyzer comprises that hydrogen peroxide, benzoyl peroxide, inorganic peroxysulfate such as ammonium persulphate or Potassium Persulphate, inorganic superphosphate such as ammonium superphosphate or potassium superphosphate, organic peracid ester are as crossing the different ester of PIVALIC ACID CRUDE (25).Oxidation-reduction system needs this oxygenant and a kind of water miscible reductive agent to combine; For example sulphur compound is such as alkali metal sulphuric acid hydrogen salt, thiosulphate or hydrosulphite, xitix, triethylamine, hydrazine, azanol, oxyacetic acid or tartrate.Generally, total consumption of catalyzer can be 0.1-2% (weight is based on total monomer weight).
Typical letex polymerization can be carried out in the presence of one or more negatively charged ion, nonionic or cationic emulsifier, as alkyl carboxylate, phosphoric acid salt, alkyl-sulphate, alkylsulfonate, the poly-vitriol of the pure and mild alkyl aryl ether of alkyl aryl ether.Usually the example of anionic emulsifier comprises alkylphenol or pure monoesters, sulfonic acid oxyethyl group alkyl phenol or ethoxy alcohol monoesters or the phosphoric acid alkoxyalkyl phenolic ester of the vitriol of basic metal or ammonium.The example of the emulsifying agent that uses comprises an alkali metal salt and 23 moles of ethylene oxide, one mole of alkyl or aryl sulfonate, lauroyl sodium sulfate, lauroyl oxyethyl group sodium sulfate of sulfuric acid nonyl phenol monoesters and has the sulfosuccinic acid alkali metal salt dibasic acid esters reaction of 6-20 carbon atom alcohol group.Nonionic emulsifier commonly used is the reacting ethylene oxide of nonyl phenolic ether and 5-23 mole.Preferably the reacting ethylene oxide of alkoxyalkyl phenol phosphoric acid salt, particularly 1 mole nonyl phenol and 5 moles obtains, acid number is 125 phosphate reaction product.Generally, total consumption of emulsifying agent is 0.01-2.0% (weight ratio is based on total water weight).
Polyreaction is carried out in a kind of redox system or a kind of elevated temperature heat technology, uses a kind of persulphate type or Diisopropyl azodicarboxylate initiator.
Generally, the temperature of carrying out polyreaction be 40-100 ℃, more suitable be 70-90 ℃, preferably 60-80 ℃, pressure is 101-308kpa (0-30psig).Thermopolymerization can be carried out in the upper end of this temperature range, is typically to be higher than 70 ℃.Be reflected in the glassware of being with condensation reflux device and carry out.This step is everlasting and is carried out in the rare gas element (as nitrogen).The time of polyreaction generally is 1-8 hour, preferably 3-4 hour.Polyreaction can be heightened the pH value of polymkeric substance to 10 after finishing, and often is 6-10.
Also use simultaneously a kind of two step polymerization techniques.
In the first step of letex polymerization, under 70-90 ℃ temperature, make the monomer mixture polymerization of 5-20% (weight), in second step, be preferably in further adding emulsifying agent after, the monomer mixture that makes remaining 80-95% carries out polymerization in the presence of polymkeric substance that the first step letex polymerization obtains.
By adding alkali final acrylate copolymer of the present invention to small part is neutralized, if necessary, can adds conventional auxiliary agent and additive to produce the water seal coating.The alkali that uses is ammonia or amine, the aqueous solution of neutralizing agent preferably, and wherein ammonia is ideal.Generally, the second step polymerization can be used identical temperature and pressure condition with the first step polymerization.A kind of seed emulsion of preparation in the first step in second step, slowly adds the residual monomer raw material up to 95% then in this emulsion, the reinforced time was at 2-5 hour.The total reaction time in second step is usually at 4-6 hour.
The example of the suitable chain-transfer agent that uses in the emulsion polymerization technique of the present invention comprises: mercaptan, polydentate compound and side chain aromatic hydrocarbon such as the different monooctyl ester of thioglycollic acid, thioglycerol, lauryl mercaptan or trimethylbenzene.Amount commonly used is between the 0.1-5% (weight is based on monomeric gross weight), and the institute that is preferably in emulsion polymerization all uses chain-transfer agent in steps.
One two step polymerization procedure is arranged in a specific embodiment of the present invention, wherein to containing up to the various polymkeric substance of 50% (weight) (as United States Patent (USP) 5, the polymkeric substance of describing in 070,164) adds raw material monomer of the present invention in seed or the core emulsion as the residual monomer raw material.
Drying, final copolymer emulsion formulations of the present invention, even once be exposed in the moisture, also can be bonded on the packaging film substrate.That is to say that it also keeps enough intrinsic bond strengths after the immersion in water.In case dry solidification, coatingsurface can not bonding undressed, uncoated film surface as undressed polypropylene or acrylic top coat.
The present invention will further describe a kind of cold sealing compositions that contains polymkeric substance at this paper.
A kind of cold sealing compositions of the present invention can comprise any multipolymer of the present invention, said composition can be a kind of aqueous solution or suspension of multipolymer, preferably its solids content is 20-40% (weight), and contain the proper auxiliary agent and the additive that are useful on conventional seal coating, comprise antiblocking additive, hydrophobizing agent, slip additive, foam inhibiting agent.Can be solid-state by adding, improve its hot smooth property through finely disintegrated, water-fast inorganic materials (as colloidal silica).Suitable antiblocking additive comprises through the mineral substance of good distribution with through the paraffin and the wax of good segmentation, the melt temperature of contained material is higher than the highest storing temp of the sealed structure that contains these materials, and is insoluble in the multipolymer of the present invention under this temperature.The example of native paraffin comprises alkane wax, Microcrystalline Wax, beeswax, Ka Naba wax (carnauba wax), Japan tallow and ceresine; The example of synthetic wax comprises hydrogenated castor oil, unichlor and long chain fatty acids amides.Above-mentioned paraffin also can improve the cold smooth property through the plastic film of coating simultaneously, and this is appreciated that film forming at room temperature slips over the ability on surface.
The cold sealed structure that the present invention also provides a kind of surface at substrate to scribble this cold sealing compositions, and this sealed structure of preserving perishable.
Before cold sealing compositions of the present invention being used the last formation of substrate (as plastic film) sealed structure of the present invention, generally pre-treatment is carried out so that coating and substrate are bonding securely in the film surface.This processing is carried out according to known technology; As by the plastic film substrate is carried out chlorination, use such as chromic acid or warm air to its carry out oxidation, by steam treatment, by corona discharge or pass through flame treating.Pretreatment process commonly used is flame treating or high-voltage corona discharge.
After the pre-treatment, the general precoating one deck of substrate surface (or two surfaces) helps fixedly basic unit's coating of top layer coating, to guarantee the bonding of coating and substrate membrane.Suitable precoating agent or basic unit's coating can be found in the literature, and it comprises such as alkyl titanate, epoxy type basic unit coating, melamine formyl and poly-piperazine.The latter especially is fit to plastic film is carried out precoating, and this is owing to contain an epoxide group at least in polystyrene emulsion.In this article, poly-piperazine can be used for the pretreated plastic film of selectivity with the form of the organic solution or the aqueous solution.In this case, the concentration of poly-piperazine can be such as 0.5% (weight) in water or the organic solution.Suitable poly-piperazinyl coating is such as DE-A-24 40 112 and US-A-3, description arranged in 753,769.
The thickness of uncoated plastic film is generally 0.015-0.060mm.Use ordinary method on plastic film, to carry out water sealing coating, as with grooved roll coating method, rolling method, dipping method, or spray or offset print technology or against roller coat cloth technology with the intaglio instrument.The excessive aqueous solution can or be got rid of scraper and remove by pressure roller.The common consumption of sealing coating is that to make the weight smooth, equally distributed coating that obtains after the drying be 1-4g/m
2
The seal coating that is coated on the plastic film carries out drying with warm air, radiant heat or other conventional instrument subsequently.This does not need to use the demoulding coating that must have in cold seal coating.
It is an important feature of the present invention that the cold sealing compositions of the present invention has low viscosity to commercially available acrylic coating, because this coating has been given polypropylene undressed and that handle through demoulding its inherent workability and impressionability.Polypropylene undressed and that handle through demoulding has workability, does not have impressionability.Emulsion coating has provided slick, a noncohesive surface, its under the operational condition of routine not can with the adhesion of acrylic top coat.But when contacting with identical coatingsurface, coatingsurface produces viscosity when pressurizeing and being heated to 66 ℃ of (150), room temperatures or being lower than room temperature (as 16 ℃ (60)), forms the intensive viscous force each other.Concerning some polymkeric substance, the bonding of generation gone back firmly than polymkeric substance itself.The temperature that sealing needs is subjected to the influence of composition coating thickness on substrate; Be that thick substrate needs high pressure sealing temperature.
Therefore, the cold sealing compositions of the present invention is in that to give strong cold seal bond intensity aspect for packing film substrate (particularly polyalkenes film, as the polypropylene screen substrate) very useful.Use this cold sealing compositions to comprise the olefin polymerization thing, as surface or directed polypropylene, co-extrusion press mold, nylon, White-opalescent film, glassine paper, paper, polyester, high density polyethylene(HDPE) and linear low density polyethylene with the special ideal substrate that obtains the cold sealed structure of the present invention.
The vinylformic acid that should comprise 80% (weight) in the polymerized unit of ideal acrylic coating at least is more preferably greater than 90% (weight).Can also contain a spot of other material such as vinyl cyanide and ethylidene vinylformic acid (ethylene acrylic acid) in acrylic acid based polymer, its content is often less than 10% (weight).Because non-acryhic material can be directed at adhesion, so often limit its content.Can add particle in the prescription of acrylic coating, be of a size of the particle of 0.5-3 micron as polyethylene, silicon and silicone, silicon-dioxide, talcum or other.
Can letex polymerization composition formula of the present invention be applied on film or the paper substrate with the technology of routine.For example, want to make substrate to soak into or when saturated, can adopt and soak or spraying.When substrate is coated with, can adopts immersion, spraying or use cylinder, painting cloth-knife, brush etc.Generally, seal in order to obtain best ripple, should use a spot of letex polymerization composition formula, the consumption on film substrate is at about 0.5-5g/6500cm
2(1000 inch
2), preferably about 1-1.5g/6500cm
2
Letex polymerization composition formula of the present invention can be used for the compound chemical combination of control surface viscosity and other surface properties with other known batching or stablizer, foam inhibiting agent, pigment auxiliary agent, dyestuff, paraffin, cereal paste, silicon-dioxide, talcum and some other or mix.Add intensifier or the thickening material viscosity with controlling polymers in polymkeric substance, making it has suitable flowability in some applications.
The seal temperature of sealed structure prepared in accordance with the present invention generally is higher than envrionment temperature.Being generally 20-80 ℃, is 30 ℃ at least better, is preferably 40-70 ℃.Heat, pressurizeing seals.In pressure process, seal coating contacts with intermeshing mode.The pressure that uses is preferably in the 6-8 crust generally at the 5-30 crust.The suitable sealing time some thousandths of second to a few tenths of second.The dry weight of seal coating is generally at 1-4g/m in film coating
2
Sealed structure prepared in accordance with the present invention (as packaging vessel) has outstanding performance aspect the intensity at the viscosity of substrate and sealing joints place.The latter is at least 250g/2.54cm.The sealing coating is appropriate to pack perishable goods especially, especially thermally sensitized food and the time management of fresh food and its can make smell keep stable.This coating and undressed plastic film (as oriented polypropylene) can adhesions.Except having good antiblocking performance, the temperature of its sealing is starkly lower than the seal temperature scope of conventional heat seal coating.General seal temperature is lower about 30 ℃ than conventional seal temperature.
The sealed package of prepared has outstanding sealing joints intensity and good surface appearance according to the present invention.Plastic film through coating has good antiblocking performance, promptly can not produce viscous force when uncoated plastic film contacts.It also has special advantage in addition, i.e. sealing can be carried out under relatively low temperature.Seal temperature generally hangs down 20-30 ℃ than the heat seal coating of routine.This can improve linear velocity under identical seal temperature.Another advantage be technology of the present invention no longer absolute demand carry out the demoulding coating at the opposite side of film, and this is that conventional cold seal coating is necessary.
Plastic film is the polyalkenes film preferably, as polyethylene and polypropylene screen.Wherein best is polypropylene screen, especially oriented polypropylene.
On the other hand, the present invention also describes the application of cold sealing compositions aspect the coat plastics film in this article.
Following embodiment is used for that the present invention will be described, and except as otherwise noted, otherwise wherein " part " is unit with weight.
Embodiment one
Present embodiment relates to the preparation of the acrylic ester emulsion (AE 1) that is used for the water seal coating.
In reaction vessel, be weighed into 31.1 parts of softening waters and 0.05 part of anionic emulsifier (ester type).Make this initial feed 80-82 ℃ of heating down.In monomer container, be weighed into 16.2 parts of methyl acrylates, 11.9 parts of methyl methacrylates, 1.4 parts of vinylformic acid, 0.5 part of different monooctyl ester of thioglycollic acid and 0.4 part of water and pre-mixing.Add 0.09 part of ammonium peroxodisulfate and 0.3 part of softening water then.In about 80 ℃, 30 minutes monomer container in 10% mixture join in the reactor quantitatively, equably, then add 0.8 part of anionic emulsifier.
Reaction mixture kept 10 minutes under temperature of reaction, then in about 80 ℃, 3 hours monomer container in remaining mixture quantitatively, join in the reactor equably.And make it 80 ℃ of following polymerizations after 2 hours, stir the mixture that adds 0.6 part of ammonia (concentration is 25%) and 6.0 parts of water down at 60 ℃.Viscosity when using the mixture (ratio of mixture is 0.6: 6.0) of ammonia (25% concentration) and water to be adjusted to solids content then to account for 30%, 25 ℃ is 30mpa.s.The content of ammonia (100%) accounts for 0.15 part in final coating (solids content accounts for 30%).
The number average molecular weight M of the acrylate copolymer that obtains
nBe 10,000, acid number is 37mgKOH/g, second-order transition temperature (T
g) be 42 ℃ (measuring) by differential scanning calorimetry meter (DSC).
Embodiment two
Present embodiment relates to the preparation of the acrylic ester emulsion (AE 2) that is used for the water seal coating.
In reaction vessel, be weighed into 20.8 parts of softening waters and 0.03 part of anionic emulsifier (ester type).Make this initial feed 80-82 ℃ of heating down.In monomer container, be weighed into 10.8 parts of methyl acrylates, 7.9 parts of methyl methacrylates, 0.9 part of vinylformic acid, 0.3 part of different monooctyl ester of thioglycollic acid and 0.2 part of water and pre-mixing.In reaction vessel, add 0.06 part of ammonium peroxodisulfate and 0.3 part of solution that softening water is made into.In about 80 ℃, 30 minutes monomer container in 10% mixture join in the retort quantitatively, equably, then add 0.56 part of anionic emulsifier.
Reaction mixture kept 10 minutes under temperature of reaction, then in about 80 ℃, 3 hours monomer container in remaining mixture quantitatively, join in the reaction vessel equably.And make it 80 ℃ of following polymerizations 2 hours.In a cut-back tank, be weighed into the mixture of 1.6 parts of ammonia (concentration is 25%) and 42.5 parts of water and be heated to 70 ℃.Under 70 ℃, reactant is flowed out.
Embodiment three
Present embodiment relates to the preparation of the acrylic ester emulsion (AE 3) that is used for the water seal coating.
ACRYLIC EMULSION AE3 prepares with the similar method of AE1, and its prescription is:
1.86 part vinylformic acid;
4.30 part methyl methacrylate;
23.34 part ethyl propenoate;
0.79 part ammonia (25% concentration); With
5.81 part water.
The number average molecular weight of the acrylate copolymer that obtains (GPC) is 10,000, and acid number is 49mgKOH/g, second-order transition temperature (T
g) be 4 ℃ (DSC).
Embodiment four
Present embodiment relates to the preparation of the acrylic ester emulsion (AE 4) that is used for the water seal coating.
ACRYLIC EMULSION AE4 prepares with the similar method of AE1, and its prescription is:
1.86 part vinylformic acid;
3.15 part vinyl cyanide;
24.49 part ethyl propenoate;
0.79 part ammonia (25% concentration); With
5.81 part water.
The number average molecular weight of the acrylate copolymer that obtains (GPC) is 10,000, and acid number is 49mgKOH/g, second-order transition temperature (T
g) be 5 ℃ (DSC).
Embodiment five
Present embodiment relates to the preparation of water seal coating (ASC1).
Get 200 parts of AE 1, add 18.0 parts of Ka Naba wax emulsions commercially available, 25% concentration (MICHEMLUBE (trade mark) 160 ex Michelman, the U.S.), continue stirring and made it homodisperse in 5 minutes, obtain ASC1 to wherein slowly stirring.
Embodiment six
Present embodiment relates to the preparation of water seal coating (ASC2).
Get 200 parts of AE 3, stick with paste (LUDOX (trade mark) AM) to wherein stirring 79.6 parts of commercially available colloid silicas of adding, continue stirring and make it homodisperse, the pH value that adds ammonia adjusting seal coating is 7.2-7.5.
Embodiment seven
Present embodiment relates to the preparation of water seal coating (ASC 3).
Get 200 parts of AE 4, add 30 parts of commercially available SYLOID (trade mark) ED 3 (aqueous solution of 5% concentration) and 30 parts of commercially available colloid silicas pastes (LUDOX (trade mark) AD 30) to wherein stirring, continue stirring and make it homodisperse, can add ammonia as needs and make the pH value of seal coating be adjusted to 7-8.
Embodiment eight
Present embodiment relates to the application of seal coating ASC 1-3.
With medical scraper coating is applied on the oriented polypropylene film 29MB210 (Belgian Mobil Plastic Europe system) that scribbles poly-piperazine basic unit, consumption is 1.5+0.2g/m
2Coated membrane is placed in HELIOS (trade mark) lab oven at, when maximum surface temperature is 95 ℃ dry 15 seconds.
These films through coating are used to measure frictional coefficient and through the resistance to blocking of coating with the uncoated film back side.In addition, measure the intensity at sealing joints place.The results are shown in table 1.Frictional coefficient
By coating direction detection frictional coefficient, measure according to working instructions in 30 minutes after the seal coating coating with ALTEK (trade mark) 9505A instrument.
Resistance to blocking can be measured with two kinds of methods: 1) 0.47 ℃ following 24 hours, 5kg/cm
2
Measure the adhesion of coating and uncoated outside surface; 2) 0.47 ℃ following 24 hours, 5kg/cm
2
Measure the adhesion of coating and acrylic acid coated outside surface;
Assess according to its separating effect, nominal value 0 shows does not have adhesion fully, and nominal value 5 shows whole adhesions.The intensity at sealing joints place
Get the wide above-mentioned polypropylene screen bars of two 25mm, seal when being 5 crust less than 80 ℃, pressure at seal temperature through coating.With the intensity of the various situation lower seal seam crossings of TESTOMETRIC (trade mark) 100 D instruments (H.Messmer buys from the human relations pier) mensuration, finding speed is 300mm/min, and width is 25mm.The results are shown in table 1.
Anti-stick non-coated surface 0.5 0.5 0.5 acrylic acid coated surperficial 0.5 11 sealed junction seam place intensity (g/25mm) the 300-400 300-400 138* that connect of table 1 ASC1 ASC2 ASC3 coefficient of friction 0.010 0.030-0.060 0.06-0.12
* the sealing joints intensity after at room temperature sealing.Embodiment nine
Present embodiment relates to preparation ACRYLIC EMULSION of the present invention (AE 5) and water seal coating (ASC 4).
Use semicontinuous proportioning process, prepare emulsion with the following method: in 2.5 hours, add the 404g raw material monomer continuously in as 30% sodium lauryl sulphate of emulsifying agent and 1.6g reactor as 70% tert-butyl hydroperoxide of free radical catalyst to 475g water, 1g are housed.Comprise the ethyl propenoate of 80.2% (weight,, together following), 15.8% vinyl cyanide, 3% methacrylic acid and the different monooctyl ester of 1% thioglycollic acid (as chain-transfer agent) in the premixed raw material monomer based on the gross weight of monomer admixture.In 3 hours, add then and contain 7g, 30% sodium lauryl sulphate, the 0.7g formyl closes the raw material of sodium hydrosulfite (as catalyst activator) and 45g water.Carry out emulsion polymerization at 60-70 ℃, reaction is to carry out in the dried inert nitrogen in the normal pressure reactor of reflux exchanger is housed.Fully stir so that the monomer homodisperse in the reactor.After adding all raw materials, the material in the reactor was kept about 1 hour.
After the polymerization, terpolymer mixes into paraffin and steatitic exemplary composition.
Make emulsion cooling subsequently and in 200 purpose filtering nets, filter.The EA/ACN/MAA terpolymer of gained has outstanding stability of emulsion.
Embodiment ten
Present embodiment relates to the preparation of cross-linked polymer (AE 6).The technological process of present embodiment except its with the thermal-initiated polymerization with embodiment nine basic identical.Use semicontinuous batch technology, prepare emulsion with the following method: in 2.5 hours, add the 406g raw material monomer continuously in as 30% sodium lauryl sulphate of emulsifying agent and 12g reactor as 10% moisture ammonium persulphate of radical initiator to 475g water, 1g are housed.Radical initiator is in the preparation of beginning polymeric eve and beginning to add the raw material monomer precontract and be added in the reactor in 2 minutes.Comprise 79.8% (weight in the premixed raw material monomer, based on the gross weight of monomer admixture, down with) ethyl propenoate, 14.8% vinyl cyanide, 3% methacrylic acid, 1% divinylbenzene (85% purity) and 1.5% the different monooctyl ester of thioglycollic acid as chain-transfer agent.In 3 hours, add then and contain 9g as 23% the Sodium dodecylbenzene sulfonate of stabilising emulsifier and the raw material of 41g water.Carry out emulsion polymerization at 75-85 ℃, reaction is to carry out in the laboratory Glass Containers identical with embodiment nine.After all raw materials added, batching kept 1 hour down at 80 ℃, added the ammoniacal liquor (being diluted with water to 400g) of 17g 30% this moment.And then temperature risen to 80 ℃ and batching was placed 1 hour again under this temperature, take out from Glass Containers the cooling back.
The character of the polymkeric substance that is made by embodiment nine and embodiment ten is listed in the table below 2:
Table 2
The polymer emulsion characteristic
Emulsion embodiment 9 embodiment, 10 total solids levels (%) 42.8 31.5 particle sizes (nm) 130 87
pH 6．1 9．5
Embodiment 11
The polymer emulsion prescription that makes according to embodiment nine and ten emulsion polymerization techniques is used for hermetic unit through acrylic acid coated standard 92 models one side by direct grooved roller coating, and this model is to scribble the poly-piperazine basic unit oriented polypropylene film of (helping the fixing coating of going up of substrate).The opposite side of film scribbles poly-piperazine basic unit and scribbles whole acroleic acid polymerization composition formulas (all-acrylic polymer formulation).Coating is dry under the temperature of 104.4 ℃ (220).
The coating wt of two pressure sealing coatings all is 1.2 (+/-0.4) g/6451.6cm
2(/ 1000 inches of 1.2 (+/-0.4) grams
2), the coating wt of acrylic coating is 0.6g/6451.6cm
2(/ 1000 inches of 0.6 grams
2).
Coated membrane is measured, and the measurement result of the cold sealing ter-polymers that measurement result and United States Patent (USP) be 5,070,164 that describe, make by one-step polymerization technology compares, and the results are shown in table 3.
Table 3
Cold seal coating result
Adhesive chemistry proportion of composing calculated value ripple seals and standard propylene surface
T
g(℃) (g/2.54cm) acid adhesion viscosity
The poly-EA/VA/ 67/30/3-5 375 of one step emulsion
*BTD is low
The polymkeric substance MAA that closes
Embodiment 9 newborn EA/ACN/ 81/16/3-5 357 21 are low
The liquid polymeric gathers MAA
Compound
Embodiment 10 newborn EA/ACN/ 81/15/3/1-5 458
*27 is low
The liquid polymeric gathers MAA/DVB
Compound
Substrate membrane: standard 92 models scribble acrylic acid oriented polypropylene film
Curl: 6.9 * 10
3N/m
2(80 pounds/inch
2), 1/2 second, room temperature
The ACN=vinyl cyanide
The EA=ethyl propenoate
The MMA=methyl methacrylate
The MAA=methacrylic acid
The BTD=adhesion destroys
The DVB=divinylbenzene
*This ripple seals the firm film that must be enough to tear, meaning has good stopping property, and promptly its binding property is also more firm than substrate membrane, but general, good ripple sealing-strength often surpasses 200g/2.54cm (200 gram/inch), is typically above 300g/2.54cm (300 gram/inch).
Claims (19)
1. multipolymer that makes by letex polymerization, it be by:
A) at least a monomer of 10-65 weight %, this monomer comprises the alkyl methacrylate of a kind of 1-12 of having a carbon atom alkyl group, a kind of vinyl aromatic hydrocarbon monomer; Or a kind of and nitrile group has the nitrile monomer of the unsaturated conjugated key of ethene, and described nitrile monomer comprises vinyl cyanide or methacrylonitrile;
And at least a following material:
B) but the softening comonomer of at least a copolymerization of 30-85 weight %, it comprises alkyl acrylate, 1,3-butadiene, vinyl-acetic ester or the vinylidene chloride with 1-12 carbon atom alkyl group; With
C) but the monomer of at least a copolymerization of 1-5 weight %, it comprises the ethylene linkage unsaturated compound that contains carboxylic acid or sulfonic acid group; Copolymerization makes,
The number-average molecular weight of the multipolymer that makes is 8,000-12, and 000, second-order transition temperature (Tg) is-35 ℃～50 ℃, and the coating that forms each other can cold sealing under pressure but can adhesion.
2. multipolymer as claimed in claim 1 is characterized in that monomer a) comprises methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate, methacrylic acid n-pentyl ester, methacrylic isoamyl valerate, N-Hexyl methacrylate, n octyl methacrylate, the own ester of methacrylic acid (2-ethyl), decyl-octyl methacrylate, methacrylic acid dodecane ester, vinylbenzene, alpha-alkyl phenylethylene, Vinyl toluene.
3. multipolymer as claimed in claim 1, it is characterized in that monomer b) comprise methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, vinylformic acid n-pentyl ester, vinylformic acid isopentyl ester, Ethyl acrylate, vinylformic acid n-octyl, Isooctyl acrylate monomer, the own ester of vinylformic acid (2-ethyl), decyl acrylate, 1,3-butadiene, vinyl-acetic ester or vinylidene chloride.
4. multipolymer as claimed in claim 1 is characterized in that monomer c) include vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, toxilic acid or methacrylic acid sulfonation ethyl ester.
5. multipolymer as claimed in claim 1 is characterized in that second-order transition temperature is-30 ℃-15 ℃.
6. multipolymer as claimed in claim 1 is characterized in that second-order transition temperature is 25 ℃-50 ℃.
7. multipolymer as claimed in claim 6, its polymerization single polymerization monomer that contains 30-55% (weight) a), the polymerization single polymerization monomer b of 40-69% (weight)), the polymerization single polymerization monomer c of 1-15% (weight)).
8. multipolymer as claimed in claim 1, it also comprises the linking agent that is selected from Vinylstyrene or 1,3 butylene glycol dimethacrylate.
9. the preparation method of multipolymer as claimed in claim 1, this method comprises:
A) make at least a monomer a) with at least a monomer b) and c) mix mutually; With
B) under the letex polymerization condition, make monomer polymerization, form described multipolymer.
10. method as claimed in claim 9, described method are to carry out in the presence of water, emulsifying agent and polymerizing catalyst.
11. method as claimed in claim 9, it is characterized in that carrying out the polymeric temperature and be 40 ℃-100 ℃, pressure is 101-308kpa.
12. method as claimed in claim 9 is characterized in that polymerization divided for two steps carried out.
13. method as claimed in claim 12, the first step that it is characterized in that described polymerization process is to be under 70 ℃-90 ℃ the monomer that accounts for monomer mixture total amount 5-20% (weight) to be carried out polymerization in temperature, and second step was is 70-90 ℃ in temperature, the monomer to remaining 80-95% (weight) in the presence of polymkeric substance that the first step obtains carries out polymerization.
14. method as claimed in claim 13 is characterized in that by adding alkali final polymkeric substance to the small part that obtains after the second step polymerization being neutralized.
15. method as claimed in claim 9 is characterized in that polymerization is to carry out in the presence of chain-transfer agent.
16. method as claimed in claim 9 is characterized in that at step a) or b) in or at step a) or b) after add a kind of additive at least, this additive is stablizer, foam inhibiting agent, drying aids, pigment, paraffin or thickening material.
17. a cold sealing compositions, it contains polymkeric substance as claimed in claim 1.
18. the composition of cold sealing as claimed in claim 17, it contains a kind of aqueous solution or suspension of this polymkeric substance.
19. the composition of cold sealing as claimed in claim 17, the solids content that it is characterized in that the aqueous solution or suspension are 20-40% (weight).
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13150093A | 1993-10-04 | 1993-10-04 | |
| US08/131,500 | 1993-10-04 | ||
| DEP4341815.5 | 1993-12-08 | ||
| DE4341815A DE4341815A1 (en) | 1993-12-08 | 1993-12-08 | Cold sealable emulsion polymer adhesive for plastic film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1136814A CN1136814A (en) | 1996-11-27 |
| CN1061356C true CN1061356C (en) | 2001-01-31 |
Family
ID=25931872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94194368A Expired - Fee Related CN1061356C (en) | 1993-10-04 | 1994-10-03 | Cold sealable cohesive polymers |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0726918A4 (en) |
| JP (1) | JPH09504815A (en) |
| CN (1) | CN1061356C (en) |
| AU (1) | AU690638B2 (en) |
| BR (1) | BR9407763A (en) |
| CA (1) | CA2172828A1 (en) |
| FI (1) | FI961500A (en) |
| NZ (1) | NZ274724A (en) |
| SG (1) | SG85572A1 (en) |
| TW (1) | TW277069B (en) |
| WO (1) | WO1995009876A1 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996011847A2 (en) * | 1994-10-11 | 1996-04-25 | Mobil Oil Corporation | Heat sealable film |
| CA2220774A1 (en) * | 1995-06-02 | 1996-12-05 | Dennis Emmett Mcgee | Heat sealable film |
| DE19632961A1 (en) * | 1996-08-16 | 1998-02-19 | Basf Lacke & Farben | Process for coating plastic parts and the plastic parts available in this way |
| DE19707185A1 (en) * | 1997-02-22 | 1998-08-27 | Ppg Industries Inc | Plastic film, its use in processes for the production of packaging containers, the packaging containers produced in this way and the use of lacquers for application via printing ink |
| US6099682A (en) * | 1998-02-09 | 2000-08-08 | 3M Innovative Properties Company Corporation Of Delaware | Cold seal package and method for making the same |
| US7279205B2 (en) | 2001-02-07 | 2007-10-09 | Sonoco Development, Inc. | Packaging material |
| US6545084B2 (en) * | 2001-02-23 | 2003-04-08 | Rohm And Haas Company | Coating composition |
| US20020160182A1 (en) * | 2001-02-23 | 2002-10-31 | Dennis Paul Lorah | Polymeric composition |
| DE10224922A1 (en) | 2002-06-04 | 2003-12-18 | Basf Ag | Process for the preparation of an aqueous copolymer solution |
| CN104449176B (en) * | 2013-02-07 | 2016-08-24 | 陈湘 | A kind of skin coating |
| CN104356840B (en) * | 2013-02-07 | 2017-02-08 | 河北晨阳工贸集团有限公司 | Coating for exterior walls of buildings |
| WO2014154507A1 (en) * | 2013-03-26 | 2014-10-02 | Basf Se | Use of a polymer dispersion for cold sealing |
| CN103242784B (en) * | 2013-05-19 | 2015-02-25 | 海南必凯水性涂料有限公司 | Acrylate copolymer emulsion paper-plastic composite adhesive and manufacturing method thereof |
| JP2017512239A (en) * | 2014-03-05 | 2017-05-18 | スリーエム イノベイティブ プロパティズ カンパニー | Skin-friendly (meth) acrylate pressure sensitive adhesive |
| US20180094174A1 (en) * | 2015-04-20 | 2018-04-05 | Basf Se | Aqueous cold seal adhesive |
| EP3344720B1 (en) | 2015-08-31 | 2020-10-14 | 3M Innovative Properties Company | Articles comprising (meth)acrylate pressure-sensitive adhesive with enhanced adhesion to wet surfaces |
| WO2017040074A1 (en) | 2015-08-31 | 2017-03-09 | 3M Innovative Properties Company | Negative pressure wound therapy dressings comprising (meth)acrylate pressure-sensitive adhesive with enhanced adhesion to wet surfaces |
| JP7400712B2 (en) * | 2018-03-23 | 2023-12-19 | 日本ゼオン株式会社 | Binder composition for non-aqueous secondary battery electrodes, conductive material paste composition for non-aqueous secondary battery electrodes, slurry composition for non-aqueous secondary battery electrodes, electrodes for non-aqueous secondary batteries, and non-aqueous secondary batteries |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5070164A (en) * | 1987-07-02 | 1991-12-03 | Mobil Oil Corporation | Cold sealable cohesive terpolymers |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2795564A (en) * | 1953-05-13 | 1957-06-11 | Rohm & Haas | Aqueous paint bases and water-base paints and process for preparing them |
| US2790735A (en) * | 1955-01-31 | 1957-04-30 | Rohm & Haas | Coated paper products and methods of making them |
| US3696082A (en) * | 1970-06-03 | 1972-10-03 | Staley Mfg Co A E | Vinylidene chloride-long chain alkyl ester polymer |
| US4000359A (en) * | 1974-12-16 | 1976-12-28 | The Goodyear Tire & Rubber Company | Interpolymer of a nitrile, vinylidene chloride and acrylate monomers |
| NL185669C (en) * | 1976-08-05 | 1990-06-18 | Mobil Oil Corp | PROCESS FOR MANUFACTURING A PACKAGING FOR A PRODUCT FROM A LAYER OF A TWO-SIDED COATED FOIL OF POLYPROPYPE. |
| US4898787A (en) * | 1987-07-02 | 1990-02-06 | Mobil Oil Corporation | Emulsion polymerized cohesive polymer latex useful as cold seal coating and improved sealable articles treated with the same |
-
1994
- 1994-10-03 NZ NZ274724A patent/NZ274724A/en unknown
- 1994-10-03 AU AU16851/95A patent/AU690638B2/en not_active Ceased
- 1994-10-03 WO PCT/US1994/011216 patent/WO1995009876A1/en not_active Application Discontinuation
- 1994-10-03 CN CN94194368A patent/CN1061356C/en not_active Expired - Fee Related
- 1994-10-03 JP JP7510971A patent/JPH09504815A/en active Pending
- 1994-10-03 SG SG9602549A patent/SG85572A1/en unknown
- 1994-10-03 BR BR9407763A patent/BR9407763A/en not_active Application Discontinuation
- 1994-10-03 CA CA002172828A patent/CA2172828A1/en not_active Abandoned
- 1994-10-03 EP EP94930017A patent/EP0726918A4/en not_active Withdrawn
- 1994-10-13 TW TW083109476A patent/TW277069B/zh active
-
1996
- 1996-04-03 FI FI961500A patent/FI961500A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5070164A (en) * | 1987-07-02 | 1991-12-03 | Mobil Oil Corporation | Cold sealable cohesive terpolymers |
Also Published As
| Publication number | Publication date |
|---|---|
| NZ274724A (en) | 1997-11-24 |
| CA2172828A1 (en) | 1995-04-13 |
| TW277069B (en) | 1996-06-01 |
| AU1685195A (en) | 1995-05-01 |
| WO1995009876A1 (en) | 1995-04-13 |
| FI961500A (en) | 1996-05-30 |
| AU690638B2 (en) | 1998-04-30 |
| JPH09504815A (en) | 1997-05-13 |
| SG85572A1 (en) | 2002-01-15 |
| EP0726918A1 (en) | 1996-08-21 |
| CN1136814A (en) | 1996-11-27 |
| BR9407763A (en) | 1997-03-18 |
| EP0726918A4 (en) | 1996-12-18 |
| FI961500A0 (en) | 1996-04-03 |
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