WO1994007966A1 - Low viscosity acrylic hot melt adhesives - Google Patents
Low viscosity acrylic hot melt adhesives Download PDFInfo
- Publication number
- WO1994007966A1 WO1994007966A1 PCT/US1993/009089 US9309089W WO9407966A1 WO 1994007966 A1 WO1994007966 A1 WO 1994007966A1 US 9309089 W US9309089 W US 9309089W WO 9407966 A1 WO9407966 A1 WO 9407966A1
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- WO
- WIPO (PCT)
- Prior art keywords
- weight
- polymer
- pressure sensitive
- sensitive adhesive
- monomers
- Prior art date
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Classifications
-
- 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
- C09J137/00—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 a heterocyclic ring containing oxygen; Adhesives based on derivatives of such polymers
-
- 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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
Definitions
- This invention relates to an acrylic hot melt pressure sensitive adhesive comprised of an alkyl acrylate copolymerized with polar monomers including amide, acid, and anhydride monomers.
- the adhesive polymer exhibits a low viscosity as formed and when reversibly cross-linked by addition of a miscible organometallic compound.
- Block copolymer rubber based hot melt pressure sensitive adhesives are well known as showing unique viscosity-temperature profiles at hot melt coating and end use temperatures.
- Rubber based hot melt pressure sensitive adhesives are typically tackified styrene- isoprene-styrene, styrene-butadiene-styrene, styrene- butadiene, and/or styrene-isoprene block copolymers.
- the styrene end blocks form physical cross-link sites or domains which can be temporarily eliminated by heating thereby allowing the rubber to flow, and to reform upon cooling for end use requirements. This reversible cross-linking contributes to the unique processability characteristics of rubber based pressure sensitive adhesives.
- Rubber based pressure sensitive adhesives have poor long term aging properties.
- known acrylic based pressure sensitive adhesives exhibit excellent aging properties.
- they do not share the unique viscosity-temperature behavior of rubber based hot melt PSA's and they are more difficult to process.
- U.S. Patent 4,360,638 disclosed a similar mechanism of polymer and metal salt interaction by adding an o- methoxy substituted aryl acid to control the viscosity and cross-linking sites. Similar mechanisms have been described in U.S. Patent 4,423,182 and U.S. Patent 4,851,278 each of said patents also incorporated herein by reference.
- the present invention is directed to acrylic hot melt pressure sensitive adhesive polymers which exhibit excellent viscosity-temperature profiles on formation and upon reversible cross-linking in situ or later and to the preparation of such adhesives by bulk polymerization techniques.
- the viscosity-temperature profiles make the adhesives compatible with equipment used for hot melt coating of rubber based pressure sensitive adhesives while providing all of the advantages of acrylic based adhesives.
- the desired viscosity temperature profile is achieved by copolymerizing into an acrylic backbone amide, anhydride, and carboxylic acid monomers which interact with an added metal cation to achieve "reversible" cross- linking properties where cross-links exist at end use temperature but are minimal at elevated temperature.
- the low viscosity, hot melt acrylic pressure sensitive adhesives of the instant invention are formed by bulk polymerization of conventional acrylic monomers containing from 4 to about 8 carbon atoms in the alkyl group and present based on the weight of the monomers, in an amount of from 60 to 95% by weight preferably from 80 to 95% by weight.
- the alkyl acrylates are copolymerized in the presence of from about 1% to about 10% by weight preferably 2 to about 6% by weight of an unsaturated carboxylic acid, and from about 1 to about 10%, preferably 2 to about 6% of an unsaturated amide monomer and positive amount up to 6% preferably from about 2 to about 4% by weight of an unsaturated anhydride monomer which, in the presence of a metal carboxylate or resinate of a metal having from a valence of from 2 to about 4, preferably 2, forms thermally reversible cross-links.
- This provides a pressure sensitive adhesive polymer which is highly fluid at elevated temperatures because of disruption of bonds between the metal cation and the polar groups and form strong reversible cohesive cross-link bonds at normal use temperature.
- tackifiers can be added in amounts of from about 5% to about 30% by weight of the total composition to enhance adhesive properties, particularly adhesion to low energy surfaces.
- the preferred alkyl acrylate is butyl acrylate; the preferred unsaturated carboxylic acid is acrylic acid; the preferred amide is N,N-dimethylacrylamide and the preferred anhydride is maleic anhydride.
- the preferred polymers include polymerized amounts of monomers having amide and carboxylic acid functionalities which synergistically give excellent viscometric and adhesive properties.
- the preferred polymer contains about 93% butyl acrylate, about 3% acrylic acid, about 2% N,N- dimethylacrylamide and about 2% maleic anhydride.
- the route to forming the hot melt bulk polymers is to form an initial reaction heel formed by stagewise in situ polymerization of a portion of the monomers by incremental addition of initiator with reactor cooling to control reaction exotherm.
- the initiator rapidly decomposes to generate free radicals for formation of the polymer heel .
- about 15 to about 20% by weight of the monomers are polymerized by stagewise addition of initiator to form the polymer heel . This is followed by continuous addition of the balance of monomers and initiator.
- Temperature is controlled by external cooling and rate of reaction to remain in the range of about 90 to about 120°C.
- the polymer product has a low viscosity as formed, generally about 2 to about 8 Pa.s at 150°C and after addition of the organometallic compound, i.e. about up to 100 Pa.s or more at 150°C enabling hot melt coating using conventional apparatus.
- the attached drawing depicts the temperature profiles from the reactants and the reactor jacket showing the region of heel formation where multiple additions of initiator is used to control, with cooling, reaction temperature and the region where monomer and initiator addition to the formed heel may be continuous or stagewise.
- hot melt, acrylic based pressure sensitive adhesives which when formed have extremely low viscosities, e.g. as low as about 2 to about 8 Pa.s at 150°C and up to about 100 Pa.s or more at 150°C when combined with a metal cation.
- low viscosity as used broadly herein there is meant a viscosity sufficiently low for coating using conventional hot melt coaters.
- the hot melt acrylic pressure sensitive adhesives have an acrylic backbone copolymerized with polar monomers which control viscosity and adhesion.
- the monomers include amide, anhydride, and carboxylic acid monomers which interact with a metal of an organometallic compound which provide thermally reversible cross-links which open when the compositions are heated to hot melt coating temperatures. This enables desirable coating of a substrate such as metal, plastic or paper.
- the cross- links reform upon cooling to provide excellent shear and other adhesive properties.
- the acrylic based hot melt adhesives of the instant invention have a glass transition temperature less than about 0°C, preferably less than about -20°C.
- Useful acrylic monomers include butylacrylate, 2-ethyl hexylacrylate, 2-methyl butylacrylate, isooctylacrylate, and the like. Butyl acrylate is presently preferred. Other monomers are or may be present .
- One monomer of necessity is an amide monomer which may be present in an amount of from about 1 to about 10% preferably about 2 to about 6% by weight of the monomers .
- the amides include acrylamide; mono and dialkylacrylamides, such as N,N-dimethylacrylamide, N-methyl acrylamide, N,N-dimethylmethacrylamide and the like.
- N,N-dimethylacrylamide is the preferred amide monomer because of the ease by which it can be mixed with other monomers used in preparing the acrylic polymer by bulk polymerization and favorable toxicological properties.
- the carboxylic acid and anhydride monomers in the polymer interact with organometallic salts such as carboxylates and resinates of metals having a valence of 2 to 4 to form reversible cross-links which give favorable low viscosity at hot melt coating temperatures and desirable higher viscosities at end use temperature.
- organometallic salts such as carboxylates and resinates of metals having a valence of 2 to 4 to form reversible cross-links which give favorable low viscosity at hot melt coating temperatures and desirable higher viscosities at end use temperature.
- Zinc octoate is the preferred organometallic salt .
- Another class of monomers of importance are carboxylic acids containing from 3 to about 5 carbon atoms such as acrylic acid, methacrylic acid, fumaric acid, itaconic acid and the like, present in an amount of from about 1% to about 10%, preferably from 2 to about 6% by weight of the monomers. They function to enhance adhesion to high energy surfaces and to synergistically cooperate with polymerized amide monomers to enhance adhesive properties and control viscosity at both end use and coating temperatures.
- Acrylic acid is the preferred carboxylic acid.
- Monomeric anhydrides preferably maleic anhydride, are typically present in a positive amount up to about 6% by weight of the total monomers preferably from 0.5 to about 6% of the total monomers and serve to control viscosity and provide additional thermally reversible cross-linking sites.
- Other monomers which are functional in the invention to modify adhesive properties include diesters of an unsaturated dicarboxylic acid, containing from 4 to 12 carbon atoms, such as dibutyl fumarate, dioctyl fumarate, dioctyl maleate and the like. Their polymerization is advantageously aided by inclusion of vinyl esters such as vinyl acetate.
- alkyl methacrylates such as methylmethacrylate and the like
- styrenic monomers such as styrene and the like.
- Polymers produced according to the invention are bulk polymerized with initiation temperatures being in the range of 80° to 100°C with polymerization occurring over a temperature range from about 90 to about 120°C to produce polymers having a viscosity in the order of about 2 to about 8 Pa.s at 150°C. They have long, stable shelf lives at ambient and elevated temperatures alone, and when combined with organometallic compounds, such as carboxylates and resinates of metals having a valence of from 2 to 4 form thermally reversible cross-links which increase viscosity up to about 100 Pa.s or more at 150°C with dramatically higher viscosities at end use temperatures. Zinc octoate is the preferred organometallic compound.
- the amount of organometallic compound can range from about 1% to about 15% by weight, preferably about 1% to about 5% by weight of the total composition.
- Calcium components may also be used as well as other di- to tetravalent metals such as aluminum, copper, tin, titanium, vanadium, chromium, calcium, magnesium, barium, cobalt, and the like.
- Metal resinates are well known in the art and disclosed as, for instance, in U.S. Patent No. 3,532,708 to Blance, incorporated herein by reference.
- the complex formed uniquely causes the bulk polymers to exhibit low viscosity (e.g. up to about 100 Pa.s at 150°C) to allow hot melt coating and high viscosities at end use temperature which are consonant with rubber based hot melt adhesives.
- Amide and acid functionalities in the polymers act synergistically to provide advantageous viscosity and adhesive properties.
- Tack can be enhanced with the addition of a small amount of conventional tackifiers such as Foral 105 and Foral 85 manufactured by Hercules, Inc. Typically, the amount of tackifier provided, if provided at all, is from 5% to about 30% by weight of the total composition.
- the acrylic hot melt pressure sensitive adhesives prepared in accordance with this invention are polymers which have too low a cohesive strength in the absence of the metal cation to be useful as a pressure sensitive adhesive but when compounded with the metal cation, and if desired, a tackifier, provide a hot melt, acrylic pressure sensitive adhesive of excellent adhesive properties at use temperatures and because of thermally reversible cross- links, are readily applicable to a variety of substrates by hot melt application techniques.
- the polymers of the instant invention are formed under essentially solvent free * conditions of bulk polymerization.
- a small charge of initiator that is in solution with the monomers is introduced into a temperature controlled reactor containing about 15 to about 20 per cent of the total monomers.
- Polymerization is initiated at a temperature of about 80 to about 100°C by heating of the monomers with the small initiator charge.
- stagewise addition of incremental amounts of initiator in solution with the monomers as shown in the Drawing to build an in situ polymer heel while maintaining a fairly even reaction temperature.
- the balance of the monomers and initiator are added to the formed polymer heel on a continuous basis or stagewise basis.
- Start up normally involves the incremental stagewise addition of three or more charges of initiator into 5 to about 20% of the total of monomers. Heating is used to initiate the reaction of the first increment of initiator to generate free radicals by decomposition of the initiator. The first charge of initiator is allowed to react almost completely. The additional charges of initiator rekindles the reaction which is controlled by size of the initiator charge and external cooling. The initiator is normally added dissolved in the monomers. A second addition is normally followed by a third and a fourth addition of initiator etc., with amounts added designed to maintain reactor temperature within a prescribed temperature range preferably about 90 to about 100°C.
- the initiator is selected to decompose at a rate which will prevent run away reaction conditions from occurring and to enable the build up of the initial polymer heel. Achieving that level of polymerization has been observed to provide a favorable "polydispersity" , namely the ratio of the weight average molecular weight to number average molecular weight (Mw/Mn) , of greater than about 5.
- the initial heel has been observed to have a polydispersity of about 2.5 increasing to above 5 typically above 5.5 by completion of the reaction.
- the high polydispersity of the final product is an indication of a high population of high molecular weight polymer units which adds substantially to provide excellent shear quality to the adhesive. We have observed that reacting only about 3% of the monomers to form a heel produces a product of too low polydispersity and inferior shear properties.
- the overall polymerization temperature can range from about 90°C to about 120°C and the product formed displays an extremely low viscosity in the absence of cross- linking.
- polymer viscosity as formed is in the order of about 2 to about 8 Pa.s at 150°C but when reversibly cross-linked with a metal ion increases to a level up to about 100 Pa.s or more at 150°C making the polymer suitable for coating using apparatus conventionally used with rubber based hot melt adhesives .
- the preferred polymer formed in accordance with the instant invention contains about 93% by weight butyl acrylate, about 3% by weight acrylic acid, about 2% by weight N,N-dimethylacrylamide and 2% by weight maleic anhydride.
- the polymers are formed in the presence of a chain transfer agent, preferably a mercaptan, with n- dodecyl mercaptan (n-DDM) being preferred.
- carboxylic acid in particular acrylic acid
- amide act synergistically to provide, as will be shown herein, unusually good viscosity and adhesive characteristics, while maleic anhydride aids in achieving low viscosity for the hot melt adhesive polymer.
- a Brookfield digital Viscometer (model RVTDV-II) equipped with a Thermosel was used to measure viscosity. The viscosity was measured at a temperature of 150 °C, using spindle 29 at 5 rpm.
- Method PSTC-1 used to measure 180° peel adhesion;
- Method PSTC-7 was used to measure shear strength (RTS) .
- RTS shear strength
- the ability of a loop of pressure-sensitive adhesive tape to adhere to a stainless steel surface instantly and without external pressure was used to measure looptack. Measurements of molecular weight were made using a Waters HPLC system equipped with Ultrastyragel columns from Columns Resolution Incorporated.
- Butyl acrylate (93 kg) , acrylic acid (3 kg) , maleic anhydride (2 kg) , N,N-dimethylacrylamide (2 kg) , and n-DDM (0.35 kg) were charged into a mix tank and stirred. After dissolving, 15 kg of this monomer mix was transferred into a jacketed reactor equipped with sensors and controllers. The reactor was then evacuated and backflushed twice with nitrogen. The remainder of the monomer mix was equally divided into two mix tanks. Vazo 52 (242.5 grams) , a free radical initiator made by DuPont, was charged into one of the tanks.
- the reactor jacket was then quickly heated to 96°C. A nitrogen bleed into the reactor was maintained during this time. When the reactor reached 82°C, the temperature rise (exotherm) became more pronounced as polymerization commenced (K-l) . Jacket temperature was quickly dropped at this moment until it reached approximately 33°C. With a set point of 90°C on the reactor, the reaction temperature reaches approximately 100°C. The centershaft of the stirrer was at 50 rpm; augers were at 150 rpm.
- reaction mass was then allowed to cool. As it approached 90°C, a second initiator charge (43.5 grams) was pumped to deliver 0.25 grams of Vazo 52 to the reactor. The introduction of this second charge (K-2) , and subsequent charges, was timed with the temperature changes of the jacket to maintain temperature between 90 and 100°C. Initiator charges are introduced when the jacket temperature begins to rise. The second charge produces a temperature rise that may approach 100°C.
- Vacuum stripping is then employed to remove the butyl acetate and any unreacted monomers.
- the resulting polymer had a viscosity of 2-8 Pa.s at 150°C.
- 400 grams of Santonox R, an antioxidant made by Monsanto was charged into the reactor.
- the cross-linking agent zinc octoate was added while the resulting polymer was still in the reactor.
- the reactor charge could also be discharged at this point for addition of the cross- linker in another vessel.
- Approximately 2.0-2.2 pphr zinc octoate was used to provide a polymer having a viscosity of approximately 100 Pa.s at 150°C.
- Table 1 shows the adhesive properties to stainless steel of the cross-linked polymer as formed.
- Example 1 Into a 10-gallon sigma blade mixer there was charged 15 kilograms of the polymer initially formed in Example 1. The mixer temperature was 150°C. A nitrogen flush was employed. The worm setting was at 1 and blade setting at 2. While mixing, 30 grams of Anti Terra U manufactured and sold by Byk Chemie, a dispersing agent and 10.5 kilograms of titanium dioxide (Tipure R-900) made by DuPont were added. Mixing was continued for 5-10 minutes, allowing for wet out of the titanium dioxide. The mix will appear "lumpy”. Zinc octoate (approximately 600-660 grams) was then added in three portions. Mixing was continued for another 30 minutes. After the titanium dioxide has become dispersed, an additional 15 kilograms of polymer was added. Mixing was allowed to continue for another 50 minutes and the mixture was discharged. Final viscosity was 100 Pa.s at 150°C.
- Tipure R-900 titanium dioxide
- Zinc octoate approximately 600-660 grams
- Table 2 compares the adhesive properties of the externally cross-linked and pigmented polymer to the in situ cross-linked polymer (Table 1) .
- the test substrate was stainless steel
- the effect of zinc octoate on polymer performance was studied.
- the polymer contained 92% butyl acrylate, 2% acrylic acid, 4% maleic anhydride and 2% acrylamide.
- Table 3 list the adhesive performance with 1-3 parts zinc octoate per 100 parts polymer. Two parts per 100 parts polymer zinc octoate was found to be the optimum level.
- An adhesive is formed as in Example 1 substituting 2- ethyl hexylacrylate for butylacrylate.
- the adhesive has better wetting ability and loop tack than an adhesive containing butyl acrylate.
- the adhesive made has a glass transition temperature of -54.3°C.
- Compounding procedures used zinc octoate for making a hot melt pressure sensitive adhesive.
- Example 10 A major market opportunity for this hot melt adhesive is in the area of industrial labels for durable goods applications. The current emphasis is geared towards having an adhesive with permanent adhesion to various substrates including metals, coated metals, and plastics. Slot coating is necessary for obtaining a good quality sample.
- the adhesive of this invention performs well for these applications and their requirements. Samples of the adhesive of Example 1, are coated on a 6" die and laminated with four different sandwich constructions at 25 g/m 2 coat weight.
- the release paper used is a platinum catalyzed siiicone release coated backing. Four facestocks are 2 mil polyester, paper, aluminum foil, and polypropylene. The last one is designed for transfer tape usage. Testing conditions included those specified in UL969. The labels formed meet Underwriters Laboratory specifications.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP93922372A EP0669965A4 (en) | 1992-09-25 | 1993-09-24 | Low viscosity acrylic hot melt adhesives. |
AU51388/93A AU675459B2 (en) | 1992-09-25 | 1993-09-24 | Low viscosity acrylic hot melt adhesives |
KR1019950701147A KR950703623A (en) | 1992-09-25 | 1993-09-24 | Low viscosity acrylic hot melt adhesive composition. |
JP6509186A JPH08504843A (en) | 1992-09-25 | 1993-09-24 | Low viscosity acrylic hot melt adhesive |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/952,074 US5252662A (en) | 1992-09-25 | 1992-09-25 | Low viscosity acrylic hot melt adhesives |
US07/952,074 | 1992-09-25 |
Publications (1)
Publication Number | Publication Date |
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WO1994007966A1 true WO1994007966A1 (en) | 1994-04-14 |
Family
ID=25492559
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1993/009089 WO1994007966A1 (en) | 1992-09-25 | 1993-09-24 | Low viscosity acrylic hot melt adhesives |
Country Status (8)
Country | Link |
---|---|
US (1) | US5252662A (en) |
EP (1) | EP0669965A4 (en) |
JP (1) | JPH08504843A (en) |
KR (1) | KR950703623A (en) |
AU (1) | AU675459B2 (en) |
CA (1) | CA2144759A1 (en) |
MX (1) | MX9305911A (en) |
WO (1) | WO1994007966A1 (en) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5637646A (en) * | 1995-12-14 | 1997-06-10 | Minnesota Mining And Manufacturing Company | Bulk radical polymerization using a batch reactor |
US6136903A (en) * | 1997-10-09 | 2000-10-24 | Avery Dennison Corporation | Repulpable, pressure-sensitive adhesive compositions |
US6720387B1 (en) | 1998-02-18 | 2004-04-13 | 3M Innovative Properties Company | Hot-melt adhesive compositions comprising acidic polymer and basic polymer blends |
US6579941B1 (en) | 2000-06-12 | 2003-06-17 | Avery Dennison Corporatoin | Adhesive compositions and constructions with outstanding cutting performance |
US7507453B2 (en) * | 2000-10-31 | 2009-03-24 | International Imaging Materials, Inc | Digital decoration and marking of glass and ceramic substrates |
US6852191B2 (en) * | 2002-08-01 | 2005-02-08 | Equipements De Transformation Imac | Method and apparatus for manufacturing pressure sensitive adhesive label stocks with printing under adhesive and product produced thereby |
US20040180208A1 (en) * | 2003-03-13 | 2004-09-16 | Bailey Michael A. | Reversibly crosslinked resin compositions and methods |
US7927703B2 (en) * | 2003-04-11 | 2011-04-19 | 3M Innovative Properties Company | Adhesive blends, articles, and methods |
US7611732B2 (en) * | 2004-07-26 | 2009-11-03 | Michael Bentley | Nutritional supplement for osteoarthritis |
JP4705768B2 (en) * | 2004-08-23 | 2011-06-22 | リンテック株式会社 | Pressure sensitive adhesive composition for polarizing film |
JP2010082102A (en) * | 2008-09-30 | 2010-04-15 | Nitto Denko Corp | Adhesive tape or sheet for application to skin, and method for producing the same |
CN102803363B (en) | 2009-06-18 | 2014-12-24 | 3M创新有限公司 | Method Of Making A Hot Melt Pressure-sensitive Adhesive |
US9315689B2 (en) | 2010-06-21 | 2016-04-19 | Basf Se | Sound damping compositions and methods for application and use |
TWI588226B (en) | 2011-10-19 | 2017-06-21 | 3M新設資產公司 | Articles with thin melt coatings and methods for making same |
BR112014019257A8 (en) | 2012-02-02 | 2017-07-11 | Avery Dennison Corp | COMPLIANT LOW CONTRACTION MODULE FILMS |
WO2018002055A1 (en) | 2016-06-28 | 2018-01-04 | Olympic Holding B.V. | Pressure sensitive adhesive tape |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3925282A (en) * | 1974-07-24 | 1975-12-09 | Nat Starch Chem Corp | Pressure sensitive hot melt adhesives |
US4354008A (en) * | 1981-05-06 | 1982-10-12 | National Starch And Chemical Corporation | Pressure sensitive, hot melt adhesives |
US4423182A (en) * | 1982-01-13 | 1983-12-27 | Rohm And Haas Company | Pressure sensitive hot melt adhesives |
US4851278A (en) * | 1986-08-11 | 1989-07-25 | Minnesota Mining And Manufacturing Company | Acrylate hot melt adhesive containing zinc carboxylate |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3032707A1 (en) * | 1980-08-30 | 1982-05-06 | Hoechst Ag, 6000 Frankfurt | THERMOPLASTIC MASS WITH INCREASED COHESION AND LOW TOWLING OF FLOW AND METHOD FOR THE PRODUCTION THEREOF |
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1992
- 1992-09-25 US US07/952,074 patent/US5252662A/en not_active Expired - Lifetime
-
1993
- 1993-09-24 KR KR1019950701147A patent/KR950703623A/en not_active Application Discontinuation
- 1993-09-24 MX MX9305911A patent/MX9305911A/en not_active IP Right Cessation
- 1993-09-24 EP EP93922372A patent/EP0669965A4/en not_active Ceased
- 1993-09-24 JP JP6509186A patent/JPH08504843A/en active Pending
- 1993-09-24 WO PCT/US1993/009089 patent/WO1994007966A1/en not_active Application Discontinuation
- 1993-09-24 CA CA002144759A patent/CA2144759A1/en not_active Abandoned
- 1993-09-24 AU AU51388/93A patent/AU675459B2/en not_active Ceased
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3925282A (en) * | 1974-07-24 | 1975-12-09 | Nat Starch Chem Corp | Pressure sensitive hot melt adhesives |
US4354008A (en) * | 1981-05-06 | 1982-10-12 | National Starch And Chemical Corporation | Pressure sensitive, hot melt adhesives |
US4423182A (en) * | 1982-01-13 | 1983-12-27 | Rohm And Haas Company | Pressure sensitive hot melt adhesives |
US4851278A (en) * | 1986-08-11 | 1989-07-25 | Minnesota Mining And Manufacturing Company | Acrylate hot melt adhesive containing zinc carboxylate |
Non-Patent Citations (1)
Title |
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See also references of EP0669965A4 * |
Also Published As
Publication number | Publication date |
---|---|
EP0669965A4 (en) | 1995-11-02 |
AU5138893A (en) | 1994-04-26 |
US5252662A (en) | 1993-10-12 |
EP0669965A1 (en) | 1995-09-06 |
KR950703623A (en) | 1995-09-20 |
CA2144759A1 (en) | 1994-04-14 |
MX9305911A (en) | 1994-05-31 |
AU675459B2 (en) | 1997-02-06 |
JPH08504843A (en) | 1996-05-28 |
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