USH509H - Preparation of adhesives - Google Patents
Preparation of adhesives Download PDFInfo
- Publication number
- USH509H USH509H US07/136,325 US13632587A USH509H US H509 H USH509 H US H509H US 13632587 A US13632587 A US 13632587A US H509 H USH509 H US H509H
- Authority
- US
- United States
- Prior art keywords
- acrylate
- tack
- weight
- oil
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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
- 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
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (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
- C09J2301/302—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 pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
Definitions
- This invention relates to the preparation of microspheres from acrylates and methacrylates, which microspheres have improved adhesive properties.
- acrylate polymers are well-known for their intrinsic adhesive properties
- the microparticles prepared according to U.S. Pat. No. 3,720,534 do not have good adhesive properties, because the polymers have too high a glass transition temperature and also the microparticles contain too much oil inside the particles.
- a tacky adhesive may be produced by polymerizing an acrylate or methacrylate. Such polymers can be deposited on bond paper and used as pressure sensitive adhesive. While the use of acrylates and methacrylates in general to form adhesives are known, it would nevertheless be advantageous to vary the level of tack. If such variations in tack level could be achieved it would be possible to produce an adhesive having an appropriate tack level required in a specific application.
- the present invention therefore, provides modified formulations so that microparticles prepared following the general procedures taught in U.S. Pat. No. 3,720,534 will have improved degrees of adhesive properties.
- a substrate support such as plastic film, foam, paper, etc.
- the coated sheets would provide from low to moderate, to high levels of adhesive strength.
- acrylates and methacrylates with approximately 4-14 carbons can be used to achieve a desired range of adhesive qualities when their corresponding homopolymers are prepared in the manner of the present invention.
- These acrylates and methacrylates have glass transition temperatures in the range of from about -15° C. to -80° C., therefore providing desirable service temperatures in the range of from about -10° C. to 40° C.
- the acrylates and methacrylates which exemplify such desirable starting materials are for example hexyl acrylate, octyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, heptyl acrylate, 1- or 2-methylbutyl acrylate, 2-methylpentyl acrylate, 6-methylnonyl acrylate, 2-ethylhexyl acrylate, and 4-methyl-2-pentyl acrylate.
- a modifying monomer such as acrylic acid, beta-carboxyl-ethyl acrylate, methacrylic acid, maleic anhydride, isobornyl acrylate, itaconic acid, and vinyl pyrrolidone can be used to increase the aggressiveness of the adhesive.
- a modifying monomer such as acrylic acid, beta-carboxyl-ethyl acrylate, methacrylic acid, maleic anhydride, isobornyl acrylate, itaconic acid, and vinyl pyrrolidone
- from about 1% to approximately 20% by weight preferrably about 1% to 10% of such a modifying monomer is advantageously used.
- acrylate or methacrylate monomers such as tetraethyleneglycol diacrylate, tetraethyleneglycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetracrylate, trimethylolpropane triacrylate, diethyleneglycol diacrylate, diethyleneglycol dimethacrylate, 1,4-butanediol dimethacrylate, and 1,3 butyleneglycol diacrylate, may be used.
- polybutene oil with a molecular weight in the range of 400 to 2,300 is particularly useful although many other oils such as dibutyl phthalate, butylbenzyl phthalate, alkylated biphenyls, alkylated naphthalenes, paraffin and isoparaffin oils, can also be used.
- the oil component will generally be used at a level of from 0 to 50% by weight of the acrylate or methacrylate monomer used.
- Polyvinyl alcohol is used as a suspension agent during polymerization in order to keep each microparticle away from the other without agglomeration.
- PVA also serves as a binder so after completing the polymerization, the microparticle slurry is ready for coating onto paper.
- PVA used in higher concentrations results in adhesives having lower tack, while if used at lower concentrations the adhesives will have higher tack, but if it were used at too low concentrations, instability of the adhesive slurry resulted and agglomeration of the microparticles occurred.
- acrylate monomer or monomer mixture 50-100 parts of an acrylate monomer or monomer mixture and 0-50 parts of an oil are stirred at room temperature for complete dissolution.
- 0.1-1.5 parts of a free radical initiator such as dicumyl peroxide, di-ter-butyl peroxide, benzoyl peroxide, or azodiisobutyronitrile is added into the solution.
- the solution is then mixed with about 100-300 parts of deoxygenerated 1.5% aqueous PVA solution. The content is allowed to react at 65°-90° C. under nitrogen, and stirred at a speed of from 500-700 rpm for about 4-24 hours to complete the polymerization.
- polyacrylate microparticles of between 5-200 microns size are obtained.
- the slurry can then be coated and dried on a substrate such as paper at a coating weight of 3-8 g/m 2 .
- the sheet can then be tested for adhesive strength using "Grams of Tack" from a Polyken Probe Tack Tester.
- the slurry was deposited on a 20# bond paper using a wire wound coating rod to deposit a dry coating weight of about 4-7 g/m 2 .
- the resultant sheet has the capacity to adhere to other surfaces the manner of a pressure sensitive adhesive label.
- the tack is 214 grams measured by a Polyken Probe Tack Tester.
- Example 1 The procedures set up in Example 1 were repeated except that the following acrylate/oil mixtures were used. Also, PVA with different molecular weights were used.
- tack levels can be achieved. Both lower and higher tack levels can be achieved by varying the make-up of the monomeric starting materials.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Adhesives comprising microparticles of acrylate copolymers are formed from higher homologs of acrylates and methacrylates. By varying the type and amount of monomers used in the starting solution the tack level may be varied. Very high tack levels are achieved with compositions made from isodecyl acrylate and 2-ethylhexyl acrylate where acrylic acid, isobornyl acrylate and vinyl pyrrolidone are included in the starting mixture and where polyvinyl alcohol is used to avoid agglomeration.
Description
This invention relates to the preparation of microspheres from acrylates and methacrylates, which microspheres have improved adhesive properties.
U.S. Pat. No. 3,720,534, which is hereby fully incorporated by reference, teaches a method of acrylate gel formation by a suspension polymerization. The polymeric microparticles have occluded in situ about 35-80% by weight of a non-volatile, non-drying oil.
Although acrylate polymers are well-known for their intrinsic adhesive properties, the microparticles prepared according to U.S. Pat. No. 3,720,534 do not have good adhesive properties, because the polymers have too high a glass transition temperature and also the microparticles contain too much oil inside the particles.
It is known prior art that a tacky adhesive may be produced by polymerizing an acrylate or methacrylate. Such polymers can be deposited on bond paper and used as pressure sensitive adhesive. While the use of acrylates and methacrylates in general to form adhesives are known, it would nevertheless be advantageous to vary the level of tack. If such variations in tack level could be achieved it would be possible to produce an adhesive having an appropriate tack level required in a specific application.
The present invention, therefore, provides modified formulations so that microparticles prepared following the general procedures taught in U.S. Pat. No. 3,720,534 will have improved degrees of adhesive properties. Thus, when these microparticles are coated onto a substrate support, such as plastic film, foam, paper, etc., the coated sheets would provide from low to moderate, to high levels of adhesive strength.
More specifically, it has now been found that variations in tack level can be achieved by using the general procedures of microsphere preparation taught in U.S. Pat. No. 3,720,534 and using a group of monomeric components similar to that previously known in the above referenced prior art formulation, except that in the present invention (1) lower oil contents are used and (2) additional modifying monomers are used.
It has been found that by making these changes a series of tack levels can be achieved allowing one to select the necessary starting components and modifiers to achieve a desired tack level.
Not only has it been possible to vary resulting tack level by making these changes, but surprisingly it has been found that certain particular combinations of acrylates and modifying monomers result in much higher than expected tack levels. Thus, when isodecyl acrylate or 2-ethylhexyl acrylate are mixed in a weight ratio of about from 99:1 to 85:15 acrylate to a modifying monomer such as acrylic acid, vinyl pyrrolidone or isobornyl acrylate unexpectedly high tack levels are achieved.
It has now been found that acrylates and methacrylates with approximately 4-14 carbons can be used to achieve a desired range of adhesive qualities when their corresponding homopolymers are prepared in the manner of the present invention. These acrylates and methacrylates have glass transition temperatures in the range of from about -15° C. to -80° C., therefore providing desirable service temperatures in the range of from about -10° C. to 40° C.
The acrylates and methacrylates which exemplify such desirable starting materials are for example hexyl acrylate, octyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, heptyl acrylate, 1- or 2-methylbutyl acrylate, 2-methylpentyl acrylate, 6-methylnonyl acrylate, 2-ethylhexyl acrylate, and 4-methyl-2-pentyl acrylate.
It has also been found that the addition of minor amounts of a modifying monomer such as acrylic acid, beta-carboxyl-ethyl acrylate, methacrylic acid, maleic anhydride, isobornyl acrylate, itaconic acid, and vinyl pyrrolidone can be used to increase the aggressiveness of the adhesive. For the purposes of the present invention, from about 1% to approximately 20% by weight, preferrably about 1% to 10% of such a modifying monomer is advantageously used.
For less aggressive adhesive applications, and in order to extend range of tack levels on the lower end, it has been found that acrylate or methacrylate monomers such as tetraethyleneglycol diacrylate, tetraethyleneglycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetracrylate, trimethylolpropane triacrylate, diethyleneglycol diacrylate, diethyleneglycol dimethacrylate, 1,4-butanediol dimethacrylate, and 1,3 butyleneglycol diacrylate, may be used.
As the oil component of the invention polybutene oil with a molecular weight in the range of 400 to 2,300 is particularly useful although many other oils such as dibutyl phthalate, butylbenzyl phthalate, alkylated biphenyls, alkylated naphthalenes, paraffin and isoparaffin oils, can also be used. The oil component will generally be used at a level of from 0 to 50% by weight of the acrylate or methacrylate monomer used.
Polyvinyl alcohol (PVA) is used as a suspension agent during polymerization in order to keep each microparticle away from the other without agglomeration. PVA also serves as a binder so after completing the polymerization, the microparticle slurry is ready for coating onto paper. PVA with about 75-90% hydrolysis with a molecular weight in the range 2,000-250,000 been found to be useful in the invention. PVA used in higher concentrations results in adhesives having lower tack, while if used at lower concentrations the adhesives will have higher tack, but if it were used at too low concentrations, instability of the adhesive slurry resulted and agglomeration of the microparticles occurred. Generally from 1 to 3% by weight based on the acrylate or methacrylate monomer will be used.
The general procedures for making microparticles will now be described.
50-100 parts of an acrylate monomer or monomer mixture and 0-50 parts of an oil are stirred at room temperature for complete dissolution. 0.1-1.5 parts of a free radical initiator such as dicumyl peroxide, di-ter-butyl peroxide, benzoyl peroxide, or azodiisobutyronitrile is added into the solution. The solution is then mixed with about 100-300 parts of deoxygenerated 1.5% aqueous PVA solution. The content is allowed to react at 65°-90° C. under nitrogen, and stirred at a speed of from 500-700 rpm for about 4-24 hours to complete the polymerization.
After polymerization, polyacrylate microparticles of between 5-200 microns size are obtained. The slurry can then be coated and dried on a substrate such as paper at a coating weight of 3-8 g/m2. The sheet can then be tested for adhesive strength using "Grams of Tack" from a Polyken Probe Tack Tester.
Using this general procedure the following experiments were run in an effort to determine the effect of varying the starting monomer, amount of oil and the amount of added modifying monomer on the tack level achieved in the final product.
114 parts of isodecylacrylate and 30 parts of Amoco polybutene oil H-1900 were stirred at room temperature until the latter was completely dissolved in the former. 6 parts of vinyl pyrrolidone was added into the solution, followed by dissolving 0.405 parts of benzoyl peroxide into it. Into a 1000 ml 4-necked flask was placed 150 parts of 1.5% aqueous Vinol 523 (a partially hydrolyzed polyvinyl alcohol from Air Products and Chemicals) solution followed by the addition of the above acrylate solution. The 4-necked flask was eqipped with a thermometer, a mechanical stirrer, a reflux condenser, and a nitrogen inlet tube. Through the reflux condenser, vacuum was applied for about 10 minutes to purge the oxygen out of the flask. Nitrogen was flushed into the solution. A nitrogen blanket was maintained during the entire polymerization reaction. After setting the mechanical stirrer at a speed of about 600 rpm, the container was heated in a heating jacket to 65°-85° C. The reaction was run for 16 hours. Microparticles ranging from 20-140 microns were obtained.
The slurry was deposited on a 20# bond paper using a wire wound coating rod to deposit a dry coating weight of about 4-7 g/m2. The resultant sheet has the capacity to adhere to other surfaces the manner of a pressure sensitive adhesive label. The tack is 214 grams measured by a Polyken Probe Tack Tester.
The procedures set up in Example 1 were repeated except that the following acrylate/oil mixtures were used. Also, PVA with different molecular weights were used.
______________________________________
Particle
(Parts) (Parts) Emul- Size Tack
Acrylate/Monomer
Oil sifier (μ) Level
______________________________________
Ex. 2 I
(120) #1 (30) V523 20-140 97
Ex. 3 I
(114)/#1 (6)
#1 (30) RX 2435
20-100 210
Ex. 4 I
(135) #3 (15) RX 2435
20-80 87
Ex. 5 II
(114)/#1 (6)
#1 (30) RX 2435
20-100 224
Ex. 6 II
(119.64)/ V523 15-200 46
#5 (0.36)
Ex. 7 I
(142.5)/#4 (7.5) V523 20-100 158
Ex. 8 I
(135) #1 (15) RX 2435
5-140 96
Ex. 9 I
(120) #2 (30) V205 10-180 107
Ex. 10 II
(119.64)/ #1 (30) RX 2435
20-180 51
#6 (0.36)
Ex. 11 I
(142.5)/#3 (7.5) V523 15-190 242
Ex. 12 I
(120) #4 (30) V523 20-100 89
Ex. 13 I
(120) #5 (30) G20-90 10-150 82
Ex. 14 II
(114)/#2 (6)
#1 (30) RX 2435
20-100 102
Ex. 15 I
(114.24)/ #1 (30) V523 10-80 49
#3 (5.4)/
#6 (0.36)
Ex. 16 I
(150) V523 80-160 88
Ex. 17 I
(130)/#7 (20) V523 20-140 211
Ex. 18 I
(140)/#7 (10) V523 20-150 198
______________________________________
Note:
In Example 2-18 the notations mean the following:
Acrylate: I = isodecyl acrylate
II = 2ethylhexyl acrylate
Modifying Monomer:
#1 = acrylic acid
#2 = maleic anhydride
#3 = vinyl pyrrolidone
#4 = betacarboxyl-ethyl acrylate
#5 = trimethylol propane triacrylate
#6 = 1,6hexanediol diacrylate
#7 = isobornyl acrylate
Oil #1 = H100 polybutene oil from Amoco Chemicals
Oil #2 = L100 polybutene oil from Amoco Chemicals
Oil #3 = dibutyl phthalate
Oil #4 = Isopar M isoparaffin oil from Exxon Chemicals
Oil #5 = Isopar G isoparaffin oil from Exxon Chemicals
PVA is polyvinyl alcohol; V205 and V523 are Vinol 205 and 523 from Air
Products and Chemicals; RX 2435 and G2090 are from Monsanto.
As can be seen from the Examples a wide range of tack levels can be achieved. Both lower and higher tack levels can be achieved by varying the make-up of the monomeric starting materials.
Claims (4)
1. An adhesive composition which comprises a copolymer of (a) isodecyl acrylate or 2-ethylhexyl acrylate, and (b) acrylic acid, or vinyl pyrrolidone, the ratio of (a) to (b) by weight being from 99:1 to 85:15.
2. An adhesive composition as in claim 1 wherein said composition consisting essentially of a copolymer of 99 parts weight isodecyl acrylate and 1 part by weight acrylic acid.
3. An adhesive composition as in claim 1 wherein said composition is a copolymer of 99 parts by weight 2-ethylhexyl acrylate and 1 part by weight acrylic acid.
4. An adhesive composition as in claim 1 wherein said composition is a copolymer of 85 parts by weight isodecyl acrylate and 15 parts by weight vinyl pyrrolidone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/136,325 USH509H (en) | 1987-12-22 | 1987-12-22 | Preparation of adhesives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/136,325 USH509H (en) | 1987-12-22 | 1987-12-22 | Preparation of adhesives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USH509H true USH509H (en) | 1988-08-02 |
Family
ID=22472348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/136,325 Abandoned USH509H (en) | 1987-12-22 | 1987-12-22 | Preparation of adhesives |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USH509H (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0352442A2 (en) * | 1988-07-27 | 1990-01-31 | Lohmann GmbH & Co. KG | Watersoluble adhesive based on polyvinylcarboxylic acids, its preparation and use |
| US4968562A (en) * | 1990-02-27 | 1990-11-06 | Minnesota Mining And Manufacturing Company | Hollow acid-free acrylate polymeric microspheres having multiple small voids |
| US5279896A (en) * | 1991-11-11 | 1994-01-18 | Nitto Denko Corporation | Heat-resistant vibration-damping pressure-sensitive adhesive composition, process for producing the same and vibration-damping adhesive tape or sheet using the composition |
| US5393800A (en) * | 1992-02-21 | 1995-02-28 | Dymax Corporation | Two-component coating formulation |
| US5458983A (en) * | 1994-07-29 | 1995-10-17 | Moore Business Forms, Inc. | Repositionable acrylate adhesive |
| US5712321A (en) * | 1996-02-01 | 1998-01-27 | Dymax Corporation | Dual-curing coating formulation and method |
| US5753362A (en) * | 1994-08-12 | 1998-05-19 | Soken Chemical & Engineering Co., Ltd. | Acrylic sheet, acrylic adhesive sheet and processes for preparing the sheets |
| US5817426A (en) * | 1996-12-04 | 1998-10-06 | Avery Dennison Corporation | Acrylic pressure-sensitive adhesives for low-energy surfaces and corrugated board |
| US6129965A (en) * | 1992-07-13 | 2000-10-10 | Moore Business Forms, Inc. | Cut sheet linerless labels |
| US6413629B1 (en) * | 1999-03-01 | 2002-07-02 | Kimoto Co., Ltd. | Easy adhesion film for transparent conductive thin film |
| US6495253B1 (en) | 1999-09-17 | 2002-12-17 | Kimoto Co., Ltd. | Support film for a transparent conductive thin film |
| US20060057366A1 (en) * | 2002-12-04 | 2006-03-16 | Marc Husemann | Poly(meth) acrylate-based pressure-sensitive adhesive |
| US20060193900A1 (en) * | 2005-02-28 | 2006-08-31 | Hisamitsu Pharmaceutical Co., Inc. | Pressure sensitive adhesive and patch |
| US20090274748A1 (en) * | 2003-06-24 | 2009-11-05 | Nipro Patch Co., Ltd | Nonaqueous pressure-sensitive adhesive for medicinal tape preparation for percutaneous absorption, medicinal tape preparation for percutaneous absorption, and process for producing the same |
| US20140175198A1 (en) * | 2012-12-21 | 2014-06-26 | Avery Dennison Corporation | Recycling Processes and Labels and Adhesives and Use Therein |
| US20170092160A1 (en) * | 2015-09-30 | 2017-03-30 | Steven N. Kruchko | Systems and Methods for Labeling |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3720534A (en) | 1964-01-29 | 1973-03-13 | Moore Business Forms Inc | Polymer gels and method of making same |
| US4243736A (en) | 1977-09-10 | 1981-01-06 | Hoechst Aktiengesellschaft | Liquid developer and copolymer polarity control agent for use therewith |
| US4510197A (en) | 1983-04-01 | 1985-04-09 | The Kendall Company | Water vapor permeable pressure sensitive adhesives incorporating modified acrylate copolymers |
-
1987
- 1987-12-22 US US07/136,325 patent/USH509H/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3720534A (en) | 1964-01-29 | 1973-03-13 | Moore Business Forms Inc | Polymer gels and method of making same |
| US4243736A (en) | 1977-09-10 | 1981-01-06 | Hoechst Aktiengesellschaft | Liquid developer and copolymer polarity control agent for use therewith |
| US4510197A (en) | 1983-04-01 | 1985-04-09 | The Kendall Company | Water vapor permeable pressure sensitive adhesives incorporating modified acrylate copolymers |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0352442A3 (en) * | 1988-07-27 | 1991-09-18 | Lohmann GmbH & Co. KG | Watersoluble adhesive based on polyvinylcarboxylic acids, its preparation and use |
| EP0352442A2 (en) * | 1988-07-27 | 1990-01-31 | Lohmann GmbH & Co. KG | Watersoluble adhesive based on polyvinylcarboxylic acids, its preparation and use |
| US4968562A (en) * | 1990-02-27 | 1990-11-06 | Minnesota Mining And Manufacturing Company | Hollow acid-free acrylate polymeric microspheres having multiple small voids |
| US5279896A (en) * | 1991-11-11 | 1994-01-18 | Nitto Denko Corporation | Heat-resistant vibration-damping pressure-sensitive adhesive composition, process for producing the same and vibration-damping adhesive tape or sheet using the composition |
| US5393800A (en) * | 1992-02-21 | 1995-02-28 | Dymax Corporation | Two-component coating formulation |
| US6129965A (en) * | 1992-07-13 | 2000-10-10 | Moore Business Forms, Inc. | Cut sheet linerless labels |
| US5458983A (en) * | 1994-07-29 | 1995-10-17 | Moore Business Forms, Inc. | Repositionable acrylate adhesive |
| US5753362A (en) * | 1994-08-12 | 1998-05-19 | Soken Chemical & Engineering Co., Ltd. | Acrylic sheet, acrylic adhesive sheet and processes for preparing the sheets |
| US5712321A (en) * | 1996-02-01 | 1998-01-27 | Dymax Corporation | Dual-curing coating formulation and method |
| US6293037B1 (en) | 1996-12-04 | 2001-09-25 | Avery Dennison Corporation | Pressure-sensitive adhesives and self-adhesive postage stamps made therewith |
| US5817426A (en) * | 1996-12-04 | 1998-10-06 | Avery Dennison Corporation | Acrylic pressure-sensitive adhesives for low-energy surfaces and corrugated board |
| US6413629B1 (en) * | 1999-03-01 | 2002-07-02 | Kimoto Co., Ltd. | Easy adhesion film for transparent conductive thin film |
| US6495253B1 (en) | 1999-09-17 | 2002-12-17 | Kimoto Co., Ltd. | Support film for a transparent conductive thin film |
| US20060057366A1 (en) * | 2002-12-04 | 2006-03-16 | Marc Husemann | Poly(meth) acrylate-based pressure-sensitive adhesive |
| US20090274748A1 (en) * | 2003-06-24 | 2009-11-05 | Nipro Patch Co., Ltd | Nonaqueous pressure-sensitive adhesive for medicinal tape preparation for percutaneous absorption, medicinal tape preparation for percutaneous absorption, and process for producing the same |
| US8962012B2 (en) | 2003-06-24 | 2015-02-24 | Nipro Patch Co., Ltd. | Nonaqueous pressure-sensitive adhesive for medicinal tape preparation for percutaneous absorption, medicinal tape preparation for percutaneous absorption, and process for producing the same |
| US20060193900A1 (en) * | 2005-02-28 | 2006-08-31 | Hisamitsu Pharmaceutical Co., Inc. | Pressure sensitive adhesive and patch |
| US20140175198A1 (en) * | 2012-12-21 | 2014-06-26 | Avery Dennison Corporation | Recycling Processes and Labels and Adhesives and Use Therein |
| US9633581B2 (en) * | 2012-12-21 | 2017-04-25 | Avery Dennison Corporation | Recycling processes and labels and adhesives and use therein |
| US20170092160A1 (en) * | 2015-09-30 | 2017-03-30 | Steven N. Kruchko | Systems and Methods for Labeling |
| US10733914B2 (en) * | 2015-09-30 | 2020-08-04 | Steven N. Kruchko | Systems and methods for labeling |
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