CA2182497A1 - Extensible flatback adhesive sheet - Google Patents
Extensible flatback adhesive sheetInfo
- Publication number
- CA2182497A1 CA2182497A1 CA002182497A CA2182497A CA2182497A1 CA 2182497 A1 CA2182497 A1 CA 2182497A1 CA 002182497 A CA002182497 A CA 002182497A CA 2182497 A CA2182497 A CA 2182497A CA 2182497 A1 CA2182497 A1 CA 2182497A1
- Authority
- CA
- Canada
- Prior art keywords
- sheet
- backing
- adhesive
- elongation
- paper
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
-
- 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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/28—Presence of paper
- C09J2400/283—Presence of paper in the substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/14—Layer or component removable to expose adhesive
- Y10T428/1462—Polymer derived from material having at least one acrylic or alkacrylic group or the nitrile or amide derivative thereof [e.g., acrylamide, acrylate ester, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2848—Three or more layers
Abstract
The present invention provides an adhesive sheet that is extensible and conformable. The sheet comprises a non-creped flatback paper backing comprising cellulosic fibers and an elastomeric saturant and having an elongation at break of at least 8 %; and an adhesive coating on at least a portion of at least one major surface of said backing. No mechanical means is used to generate extensibility or conformability in the backing of the adhesive sheet of the invention. The adhesive sheet combines all the advantages of a smooth flatback tape and the extensibility and conformability of a creped or microcreped tape.
Description
WO 95/21899 21 8 2 ~ 9 7 PCT/US9SM0271 ~YTBN8IBLIS FI~ATBACI~ ADIIE8IVE S~EET
Field of the Invention This invention relates to an adhesive sheet or assembly that is extensible and conformable. Such a sheet or assembly is useful in applications where stiffness is a concern, for example, in masking irregular or curved surfaces.
B~ck~,ou~ of th~ I~v~nt~on Paper backings are conventionally used in many pressure sensitive adhesive tapes. The paper may be impregnated with a material which is capable of binding 15 the paper fibers together to increase the tensile strength of the paper, thereby reducing the tendency of the tape to split or delaminate. A pressure sensitive adhesive is typically applied to one side of the paper sheet while a release coating is typically applied to 20 the opposite side. A barrier layer may be applied to one side of the paper as a base for the release coating, and a primer may optionally be applied to the other side of the paper to help adhere the adhesive.
The coated sheet is then wound and cut into rolls to 25 form an adhesive tape.
In many applications, it is important that the tape be extensible and conformable with minimum tape stiffness. For example, a tape used to mask curved and irregularly ~h~p~ surfaces preferably conforms closely 30 to such surfaces without tearing. In addition to being extensible and conformable, it is preferable that such tapes have relatively smooth surfaces so as to minimize the amount of adhesive and release coating required to cover the surfaces, and to minimize seepage (for 35 example, of paint) under the edge of the masking tape.
Field of the Invention This invention relates to an adhesive sheet or assembly that is extensible and conformable. Such a sheet or assembly is useful in applications where stiffness is a concern, for example, in masking irregular or curved surfaces.
B~ck~,ou~ of th~ I~v~nt~on Paper backings are conventionally used in many pressure sensitive adhesive tapes. The paper may be impregnated with a material which is capable of binding 15 the paper fibers together to increase the tensile strength of the paper, thereby reducing the tendency of the tape to split or delaminate. A pressure sensitive adhesive is typically applied to one side of the paper sheet while a release coating is typically applied to 20 the opposite side. A barrier layer may be applied to one side of the paper as a base for the release coating, and a primer may optionally be applied to the other side of the paper to help adhere the adhesive.
The coated sheet is then wound and cut into rolls to 25 form an adhesive tape.
In many applications, it is important that the tape be extensible and conformable with minimum tape stiffness. For example, a tape used to mask curved and irregularly ~h~p~ surfaces preferably conforms closely 30 to such surfaces without tearing. In addition to being extensible and conformable, it is preferable that such tapes have relatively smooth surfaces so as to minimize the amount of adhesive and release coating required to cover the surfaces, and to minimize seepage (for 35 example, of paint) under the edge of the masking tape.
2 1 8 2 ~ 9 7 PcT~sgs/on27l It is also desirable that the tape be as thin as possible to provide an improved paint edge.
Extensibility and conformability in tapes have traditionally been achieved by mechanically creping the 5 paper used in the tape backing using a creping blade to impart ridges to the paper web either before or after saturant is applied. See, for example, U.S. Patent No.
2,214,006 (Ziegler). The degree of extensibility can be further controlled by adding a rubber-resin saturant 10 to bind the fibers of the creped backing and varying the degree of vulcanization. See, for example, U.S.
Patent No. 2,410,078 (Kellgren).
The creping process and the use of a creped backing ~1ve several disadvantages associated 15 therewith. One disadvantage i6 that the creping process is difficult to ~G~ ol due to wearing of the creping blade and variations in the angle of blade used. This presents problems in maintaining product uniformity and productivity. Additionally, the degree 20 and uniform 'y of the crepe is highly depenAPnt on the moisture con_ent of the paper web, which may be difficult to control.
The creped, saturated backing also requires more adhesive and barrier or release coating to fill in the 25 valleys resulting from the creping process. In addition, the creped backing imparts a crepe image on the adhesive surface when the tape is provided in roll form, reducing the adhesive effectiveness. Finally, the ~ e~ed backing may cause irritation to the 30 applicator's fingers with prolonged use.
In contrast, a smooth backing requires less adhesive coating. In addition, the adhesive can be coated more uniformly as a continuous coating onto a smooth backing. This results in improved adhesion 35 properties when compared to comparable tapes comprising creped backing. For masking applications, a smooth WO 95/21899 2 ~ 8 2 4 9 7 PCT/llS95/00271 backing gives an improved paint edge because the adhesive can be coated more uniformly onto a smoother surface, and the adhesive surface becomes less disrupted in roll form.
To overcome the problems associated with a creped backing, several attempts have been made to either smooth out the creped surface with additional meçhAnical means, or to increase the frequency of crepe lines to impart a "fine" crepe or microcrepe texture 10 that still gives sufficient extensibility and conformability for masking applications.
U.S. Patent No. 2,941,661 (Picard) describes an impregnated and unified creped paper backing having a superfine crepe structure. The creping procedure 15 comprises the steps of subjecting a freshly formed paper web to superfine creping on a steel wet press roll using a steel creping blade which imparts at least about 40 crepe lines per lineal inch (15.7 lines per lineal cm) and calendering to reduce thickness and 20 impart a higher degree of smoothness. This compares to a conventional creped backing used in masking tapes which has about 15 to 30 crepe lines per lineal inch (5.9 to 11.8 lines per lineal cm). Picard further discloses a fine creped paper having closely spaced 25 rounded crepe ridges on one side and a number of very small cup and pocket-like indentations on the other.
U.S. Patent No. 4,849,278 (Stokes) describes a flexible paper web particularly useful as label stock for flexible, squeezable containers made by applying a fine 30 crepe pattern to a paper substrate, saturating the substrate with a soft polymer saturant at about 15 to 75 parts by weight of saturant per lOO parts of fiber weight, and calendering the web to improve the surface smoothness to improve printability. Although the 35 methods of Picard and Stokes both result in paper backings that are significantly smoother than WO 95/21899 218 2 4 9 7 PCTIUS9~/002?~
conventional creped backings, the pro~sFes till rely on a creping blade to achieve the fine creped pattern.
Thus, many of the difficulties associated with such processes (for example, blade wear, critical moisture 5 content of the web, and non-uniform crepe surfaces) remain.
Several attempts have been made to manufactur~ An extensible paper backing that does not rely on a creping blade. Generally, a compressive force is lo applied to the paper web in a direction parallel to the face surfaces of the web while simultaneously applying pressure perpendicular to said face surfaces. The pressure is applied by passing the web between rollers operating at different speeds. The compression in the 15 machine direction results in a substantial decrease in the length of the paper, while the pressure perpendicular to the web surface maintains high sheet density. Although this process does not employ a creping blade and papers made by this process are often 20 referred to as "uncreped", a mechanical means is still employed to impart fine, ~losely spaced ridges in the paper backing to give e~ .lsibility and conformability.
As a result, these backi;.~s are "creped" for purposes of the present invention. As with the creping process, 25 the moisture content of the web is still critical to maintain product uniformity. M~ch~nicms employed for obt~;ning the compressed paper web are described in several prior patents.
U.S. Patent No. 2,624,245 (Cluett), for example, 30 describes a process for the manufacture of an "uncreped" extensible paper whereby a sufficiently moist paper web is subjected to compression in a direction parallel to the surfaces of the web, while the paper is under considerable pressure perpendicular 35 to its surface to restrain it from creping. During this process, the fibers of the web are distorted and WO95/21899 218249 7 PCT~S9S/00271 crowded together, without thickening of the web. Other mechanical t~rhniques for producing an extensible paper are described in U.S. Patent No. 3,011,545 (Welsh);
U.S. Patent No. 3,329,556 (McFalls); U.S. Patent No.
5 3,359,156 (Freuler); and U.S. Patent No. 3,630,837 (Freuler); U.S. Patent No. 3,104,197 (Back); U.S.
Patent No. 4,637,859 (Trokhan); U.S. Patent No.
Extensibility and conformability in tapes have traditionally been achieved by mechanically creping the 5 paper used in the tape backing using a creping blade to impart ridges to the paper web either before or after saturant is applied. See, for example, U.S. Patent No.
2,214,006 (Ziegler). The degree of extensibility can be further controlled by adding a rubber-resin saturant 10 to bind the fibers of the creped backing and varying the degree of vulcanization. See, for example, U.S.
Patent No. 2,410,078 (Kellgren).
The creping process and the use of a creped backing ~1ve several disadvantages associated 15 therewith. One disadvantage i6 that the creping process is difficult to ~G~ ol due to wearing of the creping blade and variations in the angle of blade used. This presents problems in maintaining product uniformity and productivity. Additionally, the degree 20 and uniform 'y of the crepe is highly depenAPnt on the moisture con_ent of the paper web, which may be difficult to control.
The creped, saturated backing also requires more adhesive and barrier or release coating to fill in the 25 valleys resulting from the creping process. In addition, the creped backing imparts a crepe image on the adhesive surface when the tape is provided in roll form, reducing the adhesive effectiveness. Finally, the ~ e~ed backing may cause irritation to the 30 applicator's fingers with prolonged use.
In contrast, a smooth backing requires less adhesive coating. In addition, the adhesive can be coated more uniformly as a continuous coating onto a smooth backing. This results in improved adhesion 35 properties when compared to comparable tapes comprising creped backing. For masking applications, a smooth WO 95/21899 2 ~ 8 2 4 9 7 PCT/llS95/00271 backing gives an improved paint edge because the adhesive can be coated more uniformly onto a smoother surface, and the adhesive surface becomes less disrupted in roll form.
To overcome the problems associated with a creped backing, several attempts have been made to either smooth out the creped surface with additional meçhAnical means, or to increase the frequency of crepe lines to impart a "fine" crepe or microcrepe texture 10 that still gives sufficient extensibility and conformability for masking applications.
U.S. Patent No. 2,941,661 (Picard) describes an impregnated and unified creped paper backing having a superfine crepe structure. The creping procedure 15 comprises the steps of subjecting a freshly formed paper web to superfine creping on a steel wet press roll using a steel creping blade which imparts at least about 40 crepe lines per lineal inch (15.7 lines per lineal cm) and calendering to reduce thickness and 20 impart a higher degree of smoothness. This compares to a conventional creped backing used in masking tapes which has about 15 to 30 crepe lines per lineal inch (5.9 to 11.8 lines per lineal cm). Picard further discloses a fine creped paper having closely spaced 25 rounded crepe ridges on one side and a number of very small cup and pocket-like indentations on the other.
U.S. Patent No. 4,849,278 (Stokes) describes a flexible paper web particularly useful as label stock for flexible, squeezable containers made by applying a fine 30 crepe pattern to a paper substrate, saturating the substrate with a soft polymer saturant at about 15 to 75 parts by weight of saturant per lOO parts of fiber weight, and calendering the web to improve the surface smoothness to improve printability. Although the 35 methods of Picard and Stokes both result in paper backings that are significantly smoother than WO 95/21899 218 2 4 9 7 PCTIUS9~/002?~
conventional creped backings, the pro~sFes till rely on a creping blade to achieve the fine creped pattern.
Thus, many of the difficulties associated with such processes (for example, blade wear, critical moisture 5 content of the web, and non-uniform crepe surfaces) remain.
Several attempts have been made to manufactur~ An extensible paper backing that does not rely on a creping blade. Generally, a compressive force is lo applied to the paper web in a direction parallel to the face surfaces of the web while simultaneously applying pressure perpendicular to said face surfaces. The pressure is applied by passing the web between rollers operating at different speeds. The compression in the 15 machine direction results in a substantial decrease in the length of the paper, while the pressure perpendicular to the web surface maintains high sheet density. Although this process does not employ a creping blade and papers made by this process are often 20 referred to as "uncreped", a mechanical means is still employed to impart fine, ~losely spaced ridges in the paper backing to give e~ .lsibility and conformability.
As a result, these backi;.~s are "creped" for purposes of the present invention. As with the creping process, 25 the moisture content of the web is still critical to maintain product uniformity. M~ch~nicms employed for obt~;ning the compressed paper web are described in several prior patents.
U.S. Patent No. 2,624,245 (Cluett), for example, 30 describes a process for the manufacture of an "uncreped" extensible paper whereby a sufficiently moist paper web is subjected to compression in a direction parallel to the surfaces of the web, while the paper is under considerable pressure perpendicular 35 to its surface to restrain it from creping. During this process, the fibers of the web are distorted and WO95/21899 218249 7 PCT~S9S/00271 crowded together, without thickening of the web. Other mechanical t~rhniques for producing an extensible paper are described in U.S. Patent No. 3,011,545 (Welsh);
U.S. Patent No. 3,329,556 (McFalls); U.S. Patent No.
5 3,359,156 (Freuler); and U.S. Patent No. 3,630,837 (Freuler); U.S. Patent No. 3,104,197 (Back); U.S.
Patent No. 4,637,859 (Trokhan); U.S. Patent No.
3,503,495 (Gustafson); U.S. Patent No. 4,551,199 (Weldon); U.S. Patent No. 4,834,838 (Klowak); and U.S.
10 Patent No. 5,209,973 (Romanus Wille).
Flatback or smooth papers are commercially available. A flatback paper is one in which, once the fiber mat has been formed, it is not mechAnically disturbed to generate extensibility or conformability.
15 Flatback papers, however, are not typically employed in applications where extensibility and conformability are required as they typically exhibit elongation at break values of from about 2 to about 3%.
Various attempts have been made to increase the 20 extensibility of flatback papers. For example, vinyl-containing fibers (e.g., polyvinyl alcohol or polyvinyl chloride fibers) have been incorporated into the fiber mat. It is believed that the vinyl fibers are bonded to the cellulosic fibers in the mat by passing the mat 25 through a heated nip. Even with the addition of the vinyl fibers, however, the extensibility of the paper is only minimally increased.
A commercially available flatback tape that incorporates vinyl fibers in the paper backing, Scotch 30 Brand MAsking Tape for Sealing Applications, is available from Sumitomo 3M. The backing is saturated with styrene-butadiene/acrylate saturant. This tape is said to have an elongation at break of 7%, which is not considered to provide adequate extensibilty for masking 35 intricate configurations. The tape is marketed for linear masking tape applications.
WO95/21899 218~ 4~37 PCT/US95/00271 Other flatback tapes are known that have an elongation at break of 7-8%. These tapes also utilize a styrene-butadiene acrylate saturant. Again, however, these tapes are not considered to provide adequate 5 extensibility for masking intricate configurations.
Thus, a need still exists for an adhesive tape that has a smooth, uncreped flatback paper backing having a high degree of extensibility and conformability where no mechanical means has been used 10 to generate these properties in the backing.
Eliminating the mechAn;cal means for generating extensibility and conformability would simplify the production and reduce the cost of extensible backings, and would eliminate the variables of blade wear, 15 critical moisture content, compressible roll composition, and roller speed differential associated with creped or otherwise mechanically roughened backings. Furthermore, a flatback backing requires less adhesive, barrier and release coating and provides 20 an improved paint edge as well as improved adhesive properties.
8ummary of the Invention The present invention is directed to an adhesive 25 sheet that comprises (a) a non-creped flatback paper backing comprising cellulosic fibers and an elastomeric saturant and (b) an adhesive on at least a portion of at least one major surface of the backing. The backing has a high degree of extensibility as measured by its 30 elongation at break of greater than 8% in the length (or the machine) direction (as measured using TAPPI
st~n~rd test method T 949 om-88). The backing is not subjected to any mechAn;cal means to improve extensibility or conformability.
The adhesive sheet of the invention may be prepared by coating an adhesive onto at least a portion WO95/21899 - 21 824 9 7 PCT~S95/00271 of at least one major surface of the flatback paper backing. A primer may optionally be applied to the backing to help adhere the adhesive. When the adhesive is coated on only one side of the backing, a release 5 coating may be used on the backing opposite the adhesive so that the sheet can be dispPnsP~ in roll form. A barrier layer may also be applied to the backing as a base for the release coating. A release liner may also be included to protect the adhesive lO surface.
In another embodiment, the invention provides an adhesive sheet having an elongation at break in the length (or machine) direction greater than 8%, preferably at least 10% and more preferably at least 15 12%. The sheet comprises (a) a non-creped flatback paper backing comprising cellulosic fibers and an elastomeric saturant and (b) an adhesive on at least a portion of at least one major surface of the backing.
The backing has an elongation at break greater than 8%
20 in the length or machine direction. The backing is not subjected to any mechAnical means to improve extensibility or conformability.
In another embodiment, the present invention provides a method of masking a workpiece surface to 25 facilitate painting a first area of the surface. This method includes applying the adhesive sheet of the invention to a second area of the surface.
In another emho~iment~ the invention provides a die-cut masking assembly comprising (a) at least one 30 sheet of a non-creped flatback paper backing of a predetermined design or configuration wherein the backing comprises cellulosic fibers and an elastomeric saturant and has an elongation at break greater than 8%; (b) an adhesive coating on at least a portion of at 35 least one major surface of said backing, and (c) a release liner to which the adhesive composition is WO95/21899 ~18 2 4 ~ ~ pcT~ss5Mn27l releasably adhered, wherein no mechanical means is used to generate extensibility in the backing.
In still another embodiment, the invention provides a method of masking a workpiece surface to 5 facilitate painting a first area of the surface using die-cut masking material of the invention.
The present invention provides an adhesive sheet and assembly that is extensible and conformable.
Extensibility is herein defined as percent elongation lO at break in the length or machine directic >
Conformability is herein defined as the ability to mask the inside circumference of a three inch diameter (7.6 cm) circle without tearing the tape as detailed hereinafter in Example 3.
The adhesive sheet of the present invention can be used for masking tapes, ~i~p~r frontal tapes, autoclave tapes, medical tapes, protective sheet coatings, labels for flexible containers, or any application where an extensible and conformable adhesive tape or sheet is 20 required. The die-cut masking assembly is typically used in paint processes to mask curved, continuous surfaces. The adhesive sheet or assembly combines all the advantages of a smooth flatback tape with the extensibility and conformability of a creped or 25 microcreped tape.
Det iled Description of the Invention The flatback paper backing employs a saturant that preferably has a glass transition temperature, T" below 30 about -30C, and more preferably below about -45C.
Suitable saturants include for example, synthetic or natural isoprene, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber, acrylonitrile-butadiene-styrene rubber, crude rubber, acrylates, 35 plasticized elastomers, or combinations of elastomers WOgS/21899 ` 2 18 2 ~ PCT~S95/0027 which provide suitable fiber slippage. A preferred saturant is a latex acrylic saturant.
Preferably, the paper used in the backing has a dry basis weight of between about 23 and 33 pounds per 5 ream (37.5-54 g/m2), more preferably between about 25 and 30 pounds per ream (41-49 g/m2), and most preferably about 28 pounds per ream (46 g/m2). The paper may consist essentially of cellulosic fibers.
Alternatively, it may contain other fibers, fillers, 10 colorants and the like, such as are know in the art.
The paper is coated with saturant to give a dry coating weight preferably greater than 25 parts by weight saturant per 100 parts by weight of the paper, more preferably from about 30 to about 75 parts by weight 15 saturant per 100 parts by weight paper, most preferably from about 40 to 50 parts.
The average roughness of the backing, measured as a height and depth deviation from the center line average, is preferably less than about 7 ~m for the 20 non-creped backing of the present invention.
Conventional creped masking tape backings have an average roughness of about 12 ~m, and fine creped or microcreped backings can vary between about 3.5 and 7 ~m, dep~n~ing on the basis weight of the paper. In 25 addition, the backing preferably has a tensile strength of about 18 lbs/inch (316 N/100 mm).
Generally, a backing elongation of break of at least 6-7% is required to provide a sheet, tape or assembly that is both extensible and conformable, but 30 this level of elongation is not considered to be sufficient to mask intricate configurations. The elongation at break of the backing of the sheet of the present invention is greater than 8%. Preferably, the elongation at break of the backing is at least 10%, 35 more preferably at least 12%.
WO95/21899 2 18 2 4 9 7 pcT~sssmo27l The adhesive sheet or assembly of the present invention preferably has an elongation at break of greater than 8~. Preferably, the elongation at break of the sheet or assembly is at least lO~. This makes 5 the sheet or assembly more conformable and enables one to mask intricate configurations with less tearing. It is even more preferred that the sheet or assembly has an elongation at break of at least 12%. This level of elongation at break enables one to mask intricate lO configurations with greater ease and virtually no tearing, thereby making the masking process easier to accomplish, more efficient and less costly.
Adhesives useful in the preparation of the tape and assembly of the present invention include pressure-l5 sensitive and non-pressure sensitive adhesives, including solvent, heat, or radiation activated systems. Pressure sensitive adhesives (PSAs) are a preferred class of adhesives for use in the invention.
PSAs are normally tacky at room temperature and can be 20 adhered to a surface by the application of, at most, light finger pressure.
Useful adhesives may be based on compositions of polyacrylate; polyvinyl ether; diene-containing rubber (such as natural rubber, polyisoprene, and 25 polyisobutylene); polychloroprene; butyl rubber;
butadiene-acrylonitrile polymer; thermoplastic elastomer; block copolymers (such as the styrene-isoprene and styrene-isoprene-styrene block copolymers, ethylene-propylene-diene polymers, and styrene-30 butadiene polymer); poly-alpha-olefin; amorphous polyolefin; silicone; ethylene-containing copolymer (such as ethylene vinyl acetate, ethyl ethylacrylate, and ethyl methacrylate); polyurethane; polyamide;
epoxy; polyvinylpyrrolidone and vinylpyrrolidone 35 copolymers; polyesters; and mixtures of the above. A
general description of useful pressure-sensitive W O 9St21899 ' ~ 21 ~ 2 ~ 9 7 PCTAUS95/00271 ._ adhesives may be found in EncYclopedia of Polymer Science and Engineerinq, Vol. 13, Wiley-Interscience Publishers (New York, 1988). Additional description of useful pressure sensitive adhesives may be found in - 5 Encyclopedia of PolYmer Science and Technology, Vol. 1, Interscience Publishers (New York, 1964).
PSA compositions that are preferred for the adhesive sheet of this invention comprise an elastomeric component and a tackifier resin component, 10 wherein the tackifier component is present in an amount of from about 20 to about 300 parts by weight, preferably about 50 to about 150 parts by weight, per 100 parts by weight of the elastomeric component.
Preferred PSAs include, but are not limited to, 15 acrylate or rubber resin elastomeric components, including both natural rubber and styrene-butadiene rubber (SBR), or mixtures of the same.
To form the adhesive sheet and assembly of the present invention, the adhesive can be applied to the 20 backing by any method which results in transfer of the adhesive to, and retention thereof by, the backing.
For example, the adhesive can be applied to the paper backing by solvent coating, emulsion coating out of water, hot melt coating, or any other suitable coating 25 method. The adhesives may also be cured by any conventional method, including, for example, heat, e-beam or ultraviolet (uv) curing.
When the adhesive is coated on only one side of the backing, a release coat may be used on the backing 30 opposite the adhesive so that the adhesive sheet can be dispensed in roll form. The release coating provides a surface which is not strongly adhered to by the pressure sensitive adhesive. Conventional pressure sensitive adhesive release coatings are based on long 35 chain alkyl groups such as octadecyl isocyanate or octadecyl acrylate. Other release coatings comprise fluorocarbon, organo-silicone, æilicone, polyvinyl chloride, polyamide or melamine materials. Release coatings are typically applied in the weight range of 0.01 to 2.0 grams per square meter of backing.
A barrier layer may be applied before applying the release coating. The barrier layer preferably imparts some solvent resistance to the coated backing. The barrier layer may comprise an elastomer having a glass transition temperature (T,) from -5C to 75C. Useful 10 barrier layers include those that are based on acrylates, polyesters, styrene butadienes, styrene b ~diene-acrylonitriles, melamines, polyamides or urea f_.-maldehyde resins. The barrier layer is typically applied in the weight range of 2 to lO grams per square 15 meter of backing. Alternatively, a thermoplastic layer may be employed as a barrier layer. Representative examples of these materials include polyamide (such as nylon), and polyolefins (such as polypropylene, polyethylene, polybutylene, polybutadiene, poly-4-20 methylpentene and other polyolefins), polystyrene,polyester, copolyester, polyvinyl chloride, polyvinyl acetate, copolymers (such as ethylene/propylene copolymer, propylene/butylene copolymer, ethylene/propylene/butylene copolymer, ethylene/vinyl 25 acetate copolymer, and ethylene/butyl acrylate copolymer), polymethyl methacrylate, thermoplastic rubber block copolymer, and blends and mixtures thereof.
A primer coating may be applied to the backing 30 before applying the adhesive. Primer compositions may comprise natural rubber, SBR or neoprene rubbers, or mixtures thereof, blended with resins which are reactive and/or unreactive and filler. The primer coating is typically applied in the weight range of 2 35 to 7 grams per square meter of backing.
WO95/21899 ~1 8 2 4 9 7 PCT~S95/00271 .
The thickness of the adhesive sheet is preferably less than 5 mils (.125 mm). Such a thin sheet provides an improved paint edge in masking application.
This invention is illustrated by the following 5 examples, but the particular materials and amounts recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention.
Ex~m~le 1 This example describes a pressure sensitive tape made from a rubber resin masking adhesive comprising about 50 parts by weight crude rubber; about 50 parts 15 by weight styrene-butadiene rubber (SBR); about 60 parts by weight Sta-Tac-B~ tackifying resin, available from Reichhold Chemicals, Inc.; about 12.5 parts by weight zinc oxide; and about 1 part by weight Wingstay L~ antioxidant, available from Goodyear Tire &
20 Rubber Company. The adhesive was vulcanized with a sulfur curative.
The adhesive was applied to a backing at a dry coating weight of about 8.7 grains/24 sq.in. (36.5 g/m2) .
CA360-046 paper, a saturated and barrier coated paper available from Nonadnock Company, was employed as the backing. The CA360-046 paper had a dry basis of weight of 28 pounds per ream (46 g/m2). The paper was saturated with an acrylic latex believed to contain 30 polyethyl acrylate at a level of about 40 parts by weight per 100 parts by weight paper, to give a dry basis weight of about 40 pounds per ream (65 g/*). The paper was further coated with a barrier coating believed to contain polyethyl acrylate, polyamide 35 resin, polyvinyl chloride, ester plasticizer, and nonyl phenoxy polyethyleneoxy ethanol wetting agent. This wos5nl899 21 8 ~ ~ 9 7 pcT~sssloo27l barrier coating brought the final dry basis weight of the backing to approximately 46 pounds per ream (75 g/m2). The thickness of the backing was approximately 3.6-4.0 mils (0.09-0.1 mm) as measured using TAPPI
5 standard test method T 411 om-84. The elongation at break of the backing was approximately 14% in the machine direction, and the tensile in the machine direction was approximately 18 lbs/inch (316 N/100 mm) as measured using TAPPI standard test method T 494 om-10 88.
Adhesion values for the tape were determined asprepared and after dry heat aging for 16 hours at 150F
(66C) according to ASTN st~nA~rd test method D 3330-90 for peel adhesion of single-co~ted pressure sensitive 15 tape at 180 angle. The adhes~on values are given in Table 1.
Table 1 Peel Adhesion at 180 Angle Rubber resin adhesive oz/in. N/100 mm Initial Tack 62 68 Dry Heat Aged58 64 Comparative kxamDle 1 The same adhesive of Example 1 was coated onto a regular creped sheet identified as S-83884 available 30 from Kimberly-Clark to give a dry coating weight of 8.9 grams/24 square inches (37.3 g/m2). The S-83884 sheet is saturated with an acrylic binder and is sold for masking tape applications.
Adhesion values for the tape were determined 35 according to Example 1 and are given below in Table 2.
WO95/21899 2 ~ 8 2 ~ 9 7 PCT~S95/00271 Table 2 Peel Adhesion at 180 Angle Rllhher resin adhesive oz/in. N/100 mm Initial Tack 46 50.4 Dry Heat Aged 41 44.9 A comparison of the data of Tables 1 and 2 shows 10 that the adhesion values obtained for the tape of the present invention are higher than those of a comparable tape made with a creped paper backing.
Ex~mple 2 This example describes a pressure sensitive adhesive made from an acrylate adhesive comprising a copolymer of approximately 95.5% isooctylacrylate and 4.5% acrylic acid by weight. The adhesive was cast from heptane at about 35% solids onto the same smooth 20 paper backing described in Example 1 to give a dry coating weight of about 6.5 grains/24 sq.in. (27 g/m2).
Adhesion values for the tape were determined as in Example 1 and are given in Table 3.
Table 3 Peel Adhesion at 180 Angle Acrylate adhesive oz/in. N/100 mm 30 Initial Tack 44 48 Dry Heat Aged 42 46 Comparative Ex~mple 2 The same adhesive as described in Example 2 was applied to a commercially available creped backing (S-83884 backing available from Kimberly-Clark) at two different dry coating weights, 6.0 grains/24 sq.in.
(25.1 g/m2) and 7.5 grains/24 sq. in. (31.4 g/m2).
WO95/21899 218 2 4 9 7 PcT~sss/on271 Adhesion values for the tapes were determined as in Example 1. The results are given in Table 4.
Table 4 Peel Adhesion at 180 Angle Rubber Resin Adhesive Coating Weight In: ial Tack Dry Heat Aged grains/ g/m2 oz./ln. N/lOo oz./in. N/loo lo 24 mm mm sq.in.
6.0 25.1 24 26.3 22 24.1 7.5 31.4 32 35 31 33.9 A comparison of the data of Tables 3 and 4 shows lgher adhesion values may be obtained with the tape of .ne present invention as compared to tapes comprising a creped paper backing. The 6.5 grain/24 sq.in. (27 g/*) tape of Example 2 gave an initial tack adhesion value 20 of 44 oz/in (48 N/100 mm) and a dry heat aged adhesion value of 42 oz/in (46 N/100 mm). These values are higher than those obtained from the tapes comprising a comparable adhesive coated onto creped backing at dry coating weights of 6.0 grains/24 sq.in (25.1 g/m2) and 25 7.5 grains/24 sq.in. (31.4 g/m2).
Example 3 The 46 pound (75 g/m2) barrier coated, non-creped extensible paper backing of Examples 1 and 2 (identified as "Monadnock" in Table 5) and five other paper backings were tested to compare tensile, elongation, caliper, average surface roughness (Ra) and conformability. The five backings are described as follows:
Thilmany XKL is a microcreped or fine creped paper available from Thilmany Pulp and Paper Company.
Two different basis weights of the Thilmany paper, WO95/21899 ;~ 2 4 9 ~ pcT~ss~loo27 28 and 40 pounds per ream (46 and 65 g/m2), were tested.
KC S-46604 and KC 6750-CE are saturated paper backings available from Kimberly-Clark Corporation. KC S-46604 is a 40 pound per ream (65 g/m2) conventional creped styrene-butadiene rubber saturated paper backing, and KC 6750-CE is a 44 pound per ream (72 g/*) uncreped flatback acrylic saturated paper backing.
Potsdam MG is a 35 pound per ream (57 g/m2) machine glazed flatback paper available from Potsdam Paper Mill, Inc. In general, a "glazed" paper is dried on a highly polished drum which imparts the "glazed" surface on the side of the paper in contact with the drum.
The tensile and elongation at break in the lenght or machine direction of the six backings were tested according to TAPPI stA~AArd test methods T 494 om-88, and the calipers were measured according to TAPPI
20 stAnAArd test method T 411 om-84. The average surface roughness (Ra) in ~m was measured for both sides of each backing as an average deviation from mean using laser profilometry.
The backings were coated with a rubber resin 25 masking adhesive comprising about 50 parts by weight crude rubber, about 50 parts by weight styrene-butadiene rubber (SBR), about 60 parts by weight Sta-Tac-B~ tackifying resin available from Reichhold Chemicals, Inc., about 12.5 parts by weight zinc oxide, 30 and about 1 part by weight Wingstay L~ antioxidant, available from Goodyear Tire & Rubber Company. The adhesive was vulcanized with a sulfur curative. The adhesive was applied to each backing to provide a final dry coating weight of about 8.7 grains/24 sq.in. (36.5 35 g/m2), and each tape was tested for conformability.
woss/21899 2 i ~ 2 4 9 7 PcT~sg5/on271 Conformability was measured by the ability to mask the inside circumference of a three inch (7.6 cm) diameter circle without tearing. The procedure for measuring conformability was as follows:
The tape and a heat-cured painted steel panel having a 3 inch (7.6 cm) diameter circle printed thereon were conditioned overnight at 72F (22C) and 50% relative humidity. The testing was carried out in an environmentally controlled room at these same 10 conditions. A starting tab of the tape was grasped with the fingers of one hand, and the tape was unrolled to a distance of approximately one foot. The tape was applied to the inside circumference of the circle on the panel by fastening the starting tab at one point 15 and slowly curving the tape with one hand while pressing down the tape edge against the circle with the thumb of the other hand so as to conform the tape as closely as possible to the curvature of the circle.
~;he tape roll was held so that the unwinding tape made 20 approximately a 30 angle with the panel surface and was kept extended to a distance of approximately one foot from the panel throughout the application. A
slight outward pressure was applied as the tape was unwound from the roll so that there was always tension 25 on the tape. The process was continued around the circle until the entire inner circumference of the circle was masked.
The object of the test was to apply the tape as closely as possible to the inside circumference of the 30 circle, maintaining a smooth circle design without tearing the tape edge. A break in the circle of tape indicated that the tape was less conformable than required. Four trials were run on each tape. If more than one of the four trials resulted in a break, the 35 tape was judged to be nonconformable. The results of WO95/21899 21 82 4 9 7 PCT~S95/00271 this test, as well as those for tensile, elongation and surface roughness, are given in Table 5.
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-woss/2189s 2 1 8 2 4 g 7 PCT~S9~/00271 Results The Monadnock paper used as a backing in the tape of the present invention exhibited excellent tensile and elongation and provided a conformable tape while 5 possessing the thin caliper and surface smoothness characteristic of a flatback.
The fine creped 28 pound per ream (46 g/m2) backing from Thilmany had excellent surface smoothness and caliper, but the elongation and tensile were too low 10 for use in many masking applications. The higher basis weight fine creped Thilmany paper showed significant improvement in tensile, elongation and conformability, but the higher weight paper costs more and is thicker and stiffer, giving a boardier feel to tape made from the paper.
Backing KC S-46604 exhibited excellent tensile and elongation, but the caliper and surface roughness were higher than the other paper backings. Backing KC 6750 CE showed extremely good tensile, but low 20 elongation and poor conformability so that it could not be used for many masking applications. The glazed flatback paper from Potsdam had poor tensile as well as low elongation and poor conformability.
Only the tape of the present invention provides a 25 thin, conformable tape having a smooth surface and good physical properties (tensile and elongation), wherein no mechanical means has been applied to the backing.
10 Patent No. 5,209,973 (Romanus Wille).
Flatback or smooth papers are commercially available. A flatback paper is one in which, once the fiber mat has been formed, it is not mechAnically disturbed to generate extensibility or conformability.
15 Flatback papers, however, are not typically employed in applications where extensibility and conformability are required as they typically exhibit elongation at break values of from about 2 to about 3%.
Various attempts have been made to increase the 20 extensibility of flatback papers. For example, vinyl-containing fibers (e.g., polyvinyl alcohol or polyvinyl chloride fibers) have been incorporated into the fiber mat. It is believed that the vinyl fibers are bonded to the cellulosic fibers in the mat by passing the mat 25 through a heated nip. Even with the addition of the vinyl fibers, however, the extensibility of the paper is only minimally increased.
A commercially available flatback tape that incorporates vinyl fibers in the paper backing, Scotch 30 Brand MAsking Tape for Sealing Applications, is available from Sumitomo 3M. The backing is saturated with styrene-butadiene/acrylate saturant. This tape is said to have an elongation at break of 7%, which is not considered to provide adequate extensibilty for masking 35 intricate configurations. The tape is marketed for linear masking tape applications.
WO95/21899 218~ 4~37 PCT/US95/00271 Other flatback tapes are known that have an elongation at break of 7-8%. These tapes also utilize a styrene-butadiene acrylate saturant. Again, however, these tapes are not considered to provide adequate 5 extensibility for masking intricate configurations.
Thus, a need still exists for an adhesive tape that has a smooth, uncreped flatback paper backing having a high degree of extensibility and conformability where no mechanical means has been used 10 to generate these properties in the backing.
Eliminating the mechAn;cal means for generating extensibility and conformability would simplify the production and reduce the cost of extensible backings, and would eliminate the variables of blade wear, 15 critical moisture content, compressible roll composition, and roller speed differential associated with creped or otherwise mechanically roughened backings. Furthermore, a flatback backing requires less adhesive, barrier and release coating and provides 20 an improved paint edge as well as improved adhesive properties.
8ummary of the Invention The present invention is directed to an adhesive 25 sheet that comprises (a) a non-creped flatback paper backing comprising cellulosic fibers and an elastomeric saturant and (b) an adhesive on at least a portion of at least one major surface of the backing. The backing has a high degree of extensibility as measured by its 30 elongation at break of greater than 8% in the length (or the machine) direction (as measured using TAPPI
st~n~rd test method T 949 om-88). The backing is not subjected to any mechAn;cal means to improve extensibility or conformability.
The adhesive sheet of the invention may be prepared by coating an adhesive onto at least a portion WO95/21899 - 21 824 9 7 PCT~S95/00271 of at least one major surface of the flatback paper backing. A primer may optionally be applied to the backing to help adhere the adhesive. When the adhesive is coated on only one side of the backing, a release 5 coating may be used on the backing opposite the adhesive so that the sheet can be dispPnsP~ in roll form. A barrier layer may also be applied to the backing as a base for the release coating. A release liner may also be included to protect the adhesive lO surface.
In another embodiment, the invention provides an adhesive sheet having an elongation at break in the length (or machine) direction greater than 8%, preferably at least 10% and more preferably at least 15 12%. The sheet comprises (a) a non-creped flatback paper backing comprising cellulosic fibers and an elastomeric saturant and (b) an adhesive on at least a portion of at least one major surface of the backing.
The backing has an elongation at break greater than 8%
20 in the length or machine direction. The backing is not subjected to any mechAnical means to improve extensibility or conformability.
In another embodiment, the present invention provides a method of masking a workpiece surface to 25 facilitate painting a first area of the surface. This method includes applying the adhesive sheet of the invention to a second area of the surface.
In another emho~iment~ the invention provides a die-cut masking assembly comprising (a) at least one 30 sheet of a non-creped flatback paper backing of a predetermined design or configuration wherein the backing comprises cellulosic fibers and an elastomeric saturant and has an elongation at break greater than 8%; (b) an adhesive coating on at least a portion of at 35 least one major surface of said backing, and (c) a release liner to which the adhesive composition is WO95/21899 ~18 2 4 ~ ~ pcT~ss5Mn27l releasably adhered, wherein no mechanical means is used to generate extensibility in the backing.
In still another embodiment, the invention provides a method of masking a workpiece surface to 5 facilitate painting a first area of the surface using die-cut masking material of the invention.
The present invention provides an adhesive sheet and assembly that is extensible and conformable.
Extensibility is herein defined as percent elongation lO at break in the length or machine directic >
Conformability is herein defined as the ability to mask the inside circumference of a three inch diameter (7.6 cm) circle without tearing the tape as detailed hereinafter in Example 3.
The adhesive sheet of the present invention can be used for masking tapes, ~i~p~r frontal tapes, autoclave tapes, medical tapes, protective sheet coatings, labels for flexible containers, or any application where an extensible and conformable adhesive tape or sheet is 20 required. The die-cut masking assembly is typically used in paint processes to mask curved, continuous surfaces. The adhesive sheet or assembly combines all the advantages of a smooth flatback tape with the extensibility and conformability of a creped or 25 microcreped tape.
Det iled Description of the Invention The flatback paper backing employs a saturant that preferably has a glass transition temperature, T" below 30 about -30C, and more preferably below about -45C.
Suitable saturants include for example, synthetic or natural isoprene, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber, acrylonitrile-butadiene-styrene rubber, crude rubber, acrylates, 35 plasticized elastomers, or combinations of elastomers WOgS/21899 ` 2 18 2 ~ PCT~S95/0027 which provide suitable fiber slippage. A preferred saturant is a latex acrylic saturant.
Preferably, the paper used in the backing has a dry basis weight of between about 23 and 33 pounds per 5 ream (37.5-54 g/m2), more preferably between about 25 and 30 pounds per ream (41-49 g/m2), and most preferably about 28 pounds per ream (46 g/m2). The paper may consist essentially of cellulosic fibers.
Alternatively, it may contain other fibers, fillers, 10 colorants and the like, such as are know in the art.
The paper is coated with saturant to give a dry coating weight preferably greater than 25 parts by weight saturant per 100 parts by weight of the paper, more preferably from about 30 to about 75 parts by weight 15 saturant per 100 parts by weight paper, most preferably from about 40 to 50 parts.
The average roughness of the backing, measured as a height and depth deviation from the center line average, is preferably less than about 7 ~m for the 20 non-creped backing of the present invention.
Conventional creped masking tape backings have an average roughness of about 12 ~m, and fine creped or microcreped backings can vary between about 3.5 and 7 ~m, dep~n~ing on the basis weight of the paper. In 25 addition, the backing preferably has a tensile strength of about 18 lbs/inch (316 N/100 mm).
Generally, a backing elongation of break of at least 6-7% is required to provide a sheet, tape or assembly that is both extensible and conformable, but 30 this level of elongation is not considered to be sufficient to mask intricate configurations. The elongation at break of the backing of the sheet of the present invention is greater than 8%. Preferably, the elongation at break of the backing is at least 10%, 35 more preferably at least 12%.
WO95/21899 2 18 2 4 9 7 pcT~sssmo27l The adhesive sheet or assembly of the present invention preferably has an elongation at break of greater than 8~. Preferably, the elongation at break of the sheet or assembly is at least lO~. This makes 5 the sheet or assembly more conformable and enables one to mask intricate configurations with less tearing. It is even more preferred that the sheet or assembly has an elongation at break of at least 12%. This level of elongation at break enables one to mask intricate lO configurations with greater ease and virtually no tearing, thereby making the masking process easier to accomplish, more efficient and less costly.
Adhesives useful in the preparation of the tape and assembly of the present invention include pressure-l5 sensitive and non-pressure sensitive adhesives, including solvent, heat, or radiation activated systems. Pressure sensitive adhesives (PSAs) are a preferred class of adhesives for use in the invention.
PSAs are normally tacky at room temperature and can be 20 adhered to a surface by the application of, at most, light finger pressure.
Useful adhesives may be based on compositions of polyacrylate; polyvinyl ether; diene-containing rubber (such as natural rubber, polyisoprene, and 25 polyisobutylene); polychloroprene; butyl rubber;
butadiene-acrylonitrile polymer; thermoplastic elastomer; block copolymers (such as the styrene-isoprene and styrene-isoprene-styrene block copolymers, ethylene-propylene-diene polymers, and styrene-30 butadiene polymer); poly-alpha-olefin; amorphous polyolefin; silicone; ethylene-containing copolymer (such as ethylene vinyl acetate, ethyl ethylacrylate, and ethyl methacrylate); polyurethane; polyamide;
epoxy; polyvinylpyrrolidone and vinylpyrrolidone 35 copolymers; polyesters; and mixtures of the above. A
general description of useful pressure-sensitive W O 9St21899 ' ~ 21 ~ 2 ~ 9 7 PCTAUS95/00271 ._ adhesives may be found in EncYclopedia of Polymer Science and Engineerinq, Vol. 13, Wiley-Interscience Publishers (New York, 1988). Additional description of useful pressure sensitive adhesives may be found in - 5 Encyclopedia of PolYmer Science and Technology, Vol. 1, Interscience Publishers (New York, 1964).
PSA compositions that are preferred for the adhesive sheet of this invention comprise an elastomeric component and a tackifier resin component, 10 wherein the tackifier component is present in an amount of from about 20 to about 300 parts by weight, preferably about 50 to about 150 parts by weight, per 100 parts by weight of the elastomeric component.
Preferred PSAs include, but are not limited to, 15 acrylate or rubber resin elastomeric components, including both natural rubber and styrene-butadiene rubber (SBR), or mixtures of the same.
To form the adhesive sheet and assembly of the present invention, the adhesive can be applied to the 20 backing by any method which results in transfer of the adhesive to, and retention thereof by, the backing.
For example, the adhesive can be applied to the paper backing by solvent coating, emulsion coating out of water, hot melt coating, or any other suitable coating 25 method. The adhesives may also be cured by any conventional method, including, for example, heat, e-beam or ultraviolet (uv) curing.
When the adhesive is coated on only one side of the backing, a release coat may be used on the backing 30 opposite the adhesive so that the adhesive sheet can be dispensed in roll form. The release coating provides a surface which is not strongly adhered to by the pressure sensitive adhesive. Conventional pressure sensitive adhesive release coatings are based on long 35 chain alkyl groups such as octadecyl isocyanate or octadecyl acrylate. Other release coatings comprise fluorocarbon, organo-silicone, æilicone, polyvinyl chloride, polyamide or melamine materials. Release coatings are typically applied in the weight range of 0.01 to 2.0 grams per square meter of backing.
A barrier layer may be applied before applying the release coating. The barrier layer preferably imparts some solvent resistance to the coated backing. The barrier layer may comprise an elastomer having a glass transition temperature (T,) from -5C to 75C. Useful 10 barrier layers include those that are based on acrylates, polyesters, styrene butadienes, styrene b ~diene-acrylonitriles, melamines, polyamides or urea f_.-maldehyde resins. The barrier layer is typically applied in the weight range of 2 to lO grams per square 15 meter of backing. Alternatively, a thermoplastic layer may be employed as a barrier layer. Representative examples of these materials include polyamide (such as nylon), and polyolefins (such as polypropylene, polyethylene, polybutylene, polybutadiene, poly-4-20 methylpentene and other polyolefins), polystyrene,polyester, copolyester, polyvinyl chloride, polyvinyl acetate, copolymers (such as ethylene/propylene copolymer, propylene/butylene copolymer, ethylene/propylene/butylene copolymer, ethylene/vinyl 25 acetate copolymer, and ethylene/butyl acrylate copolymer), polymethyl methacrylate, thermoplastic rubber block copolymer, and blends and mixtures thereof.
A primer coating may be applied to the backing 30 before applying the adhesive. Primer compositions may comprise natural rubber, SBR or neoprene rubbers, or mixtures thereof, blended with resins which are reactive and/or unreactive and filler. The primer coating is typically applied in the weight range of 2 35 to 7 grams per square meter of backing.
WO95/21899 ~1 8 2 4 9 7 PCT~S95/00271 .
The thickness of the adhesive sheet is preferably less than 5 mils (.125 mm). Such a thin sheet provides an improved paint edge in masking application.
This invention is illustrated by the following 5 examples, but the particular materials and amounts recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention.
Ex~m~le 1 This example describes a pressure sensitive tape made from a rubber resin masking adhesive comprising about 50 parts by weight crude rubber; about 50 parts 15 by weight styrene-butadiene rubber (SBR); about 60 parts by weight Sta-Tac-B~ tackifying resin, available from Reichhold Chemicals, Inc.; about 12.5 parts by weight zinc oxide; and about 1 part by weight Wingstay L~ antioxidant, available from Goodyear Tire &
20 Rubber Company. The adhesive was vulcanized with a sulfur curative.
The adhesive was applied to a backing at a dry coating weight of about 8.7 grains/24 sq.in. (36.5 g/m2) .
CA360-046 paper, a saturated and barrier coated paper available from Nonadnock Company, was employed as the backing. The CA360-046 paper had a dry basis of weight of 28 pounds per ream (46 g/m2). The paper was saturated with an acrylic latex believed to contain 30 polyethyl acrylate at a level of about 40 parts by weight per 100 parts by weight paper, to give a dry basis weight of about 40 pounds per ream (65 g/*). The paper was further coated with a barrier coating believed to contain polyethyl acrylate, polyamide 35 resin, polyvinyl chloride, ester plasticizer, and nonyl phenoxy polyethyleneoxy ethanol wetting agent. This wos5nl899 21 8 ~ ~ 9 7 pcT~sssloo27l barrier coating brought the final dry basis weight of the backing to approximately 46 pounds per ream (75 g/m2). The thickness of the backing was approximately 3.6-4.0 mils (0.09-0.1 mm) as measured using TAPPI
5 standard test method T 411 om-84. The elongation at break of the backing was approximately 14% in the machine direction, and the tensile in the machine direction was approximately 18 lbs/inch (316 N/100 mm) as measured using TAPPI standard test method T 494 om-10 88.
Adhesion values for the tape were determined asprepared and after dry heat aging for 16 hours at 150F
(66C) according to ASTN st~nA~rd test method D 3330-90 for peel adhesion of single-co~ted pressure sensitive 15 tape at 180 angle. The adhes~on values are given in Table 1.
Table 1 Peel Adhesion at 180 Angle Rubber resin adhesive oz/in. N/100 mm Initial Tack 62 68 Dry Heat Aged58 64 Comparative kxamDle 1 The same adhesive of Example 1 was coated onto a regular creped sheet identified as S-83884 available 30 from Kimberly-Clark to give a dry coating weight of 8.9 grams/24 square inches (37.3 g/m2). The S-83884 sheet is saturated with an acrylic binder and is sold for masking tape applications.
Adhesion values for the tape were determined 35 according to Example 1 and are given below in Table 2.
WO95/21899 2 ~ 8 2 ~ 9 7 PCT~S95/00271 Table 2 Peel Adhesion at 180 Angle Rllhher resin adhesive oz/in. N/100 mm Initial Tack 46 50.4 Dry Heat Aged 41 44.9 A comparison of the data of Tables 1 and 2 shows 10 that the adhesion values obtained for the tape of the present invention are higher than those of a comparable tape made with a creped paper backing.
Ex~mple 2 This example describes a pressure sensitive adhesive made from an acrylate adhesive comprising a copolymer of approximately 95.5% isooctylacrylate and 4.5% acrylic acid by weight. The adhesive was cast from heptane at about 35% solids onto the same smooth 20 paper backing described in Example 1 to give a dry coating weight of about 6.5 grains/24 sq.in. (27 g/m2).
Adhesion values for the tape were determined as in Example 1 and are given in Table 3.
Table 3 Peel Adhesion at 180 Angle Acrylate adhesive oz/in. N/100 mm 30 Initial Tack 44 48 Dry Heat Aged 42 46 Comparative Ex~mple 2 The same adhesive as described in Example 2 was applied to a commercially available creped backing (S-83884 backing available from Kimberly-Clark) at two different dry coating weights, 6.0 grains/24 sq.in.
(25.1 g/m2) and 7.5 grains/24 sq. in. (31.4 g/m2).
WO95/21899 218 2 4 9 7 PcT~sss/on271 Adhesion values for the tapes were determined as in Example 1. The results are given in Table 4.
Table 4 Peel Adhesion at 180 Angle Rubber Resin Adhesive Coating Weight In: ial Tack Dry Heat Aged grains/ g/m2 oz./ln. N/lOo oz./in. N/loo lo 24 mm mm sq.in.
6.0 25.1 24 26.3 22 24.1 7.5 31.4 32 35 31 33.9 A comparison of the data of Tables 3 and 4 shows lgher adhesion values may be obtained with the tape of .ne present invention as compared to tapes comprising a creped paper backing. The 6.5 grain/24 sq.in. (27 g/*) tape of Example 2 gave an initial tack adhesion value 20 of 44 oz/in (48 N/100 mm) and a dry heat aged adhesion value of 42 oz/in (46 N/100 mm). These values are higher than those obtained from the tapes comprising a comparable adhesive coated onto creped backing at dry coating weights of 6.0 grains/24 sq.in (25.1 g/m2) and 25 7.5 grains/24 sq.in. (31.4 g/m2).
Example 3 The 46 pound (75 g/m2) barrier coated, non-creped extensible paper backing of Examples 1 and 2 (identified as "Monadnock" in Table 5) and five other paper backings were tested to compare tensile, elongation, caliper, average surface roughness (Ra) and conformability. The five backings are described as follows:
Thilmany XKL is a microcreped or fine creped paper available from Thilmany Pulp and Paper Company.
Two different basis weights of the Thilmany paper, WO95/21899 ;~ 2 4 9 ~ pcT~ss~loo27 28 and 40 pounds per ream (46 and 65 g/m2), were tested.
KC S-46604 and KC 6750-CE are saturated paper backings available from Kimberly-Clark Corporation. KC S-46604 is a 40 pound per ream (65 g/m2) conventional creped styrene-butadiene rubber saturated paper backing, and KC 6750-CE is a 44 pound per ream (72 g/*) uncreped flatback acrylic saturated paper backing.
Potsdam MG is a 35 pound per ream (57 g/m2) machine glazed flatback paper available from Potsdam Paper Mill, Inc. In general, a "glazed" paper is dried on a highly polished drum which imparts the "glazed" surface on the side of the paper in contact with the drum.
The tensile and elongation at break in the lenght or machine direction of the six backings were tested according to TAPPI stA~AArd test methods T 494 om-88, and the calipers were measured according to TAPPI
20 stAnAArd test method T 411 om-84. The average surface roughness (Ra) in ~m was measured for both sides of each backing as an average deviation from mean using laser profilometry.
The backings were coated with a rubber resin 25 masking adhesive comprising about 50 parts by weight crude rubber, about 50 parts by weight styrene-butadiene rubber (SBR), about 60 parts by weight Sta-Tac-B~ tackifying resin available from Reichhold Chemicals, Inc., about 12.5 parts by weight zinc oxide, 30 and about 1 part by weight Wingstay L~ antioxidant, available from Goodyear Tire & Rubber Company. The adhesive was vulcanized with a sulfur curative. The adhesive was applied to each backing to provide a final dry coating weight of about 8.7 grains/24 sq.in. (36.5 35 g/m2), and each tape was tested for conformability.
woss/21899 2 i ~ 2 4 9 7 PcT~sg5/on271 Conformability was measured by the ability to mask the inside circumference of a three inch (7.6 cm) diameter circle without tearing. The procedure for measuring conformability was as follows:
The tape and a heat-cured painted steel panel having a 3 inch (7.6 cm) diameter circle printed thereon were conditioned overnight at 72F (22C) and 50% relative humidity. The testing was carried out in an environmentally controlled room at these same 10 conditions. A starting tab of the tape was grasped with the fingers of one hand, and the tape was unrolled to a distance of approximately one foot. The tape was applied to the inside circumference of the circle on the panel by fastening the starting tab at one point 15 and slowly curving the tape with one hand while pressing down the tape edge against the circle with the thumb of the other hand so as to conform the tape as closely as possible to the curvature of the circle.
~;he tape roll was held so that the unwinding tape made 20 approximately a 30 angle with the panel surface and was kept extended to a distance of approximately one foot from the panel throughout the application. A
slight outward pressure was applied as the tape was unwound from the roll so that there was always tension 25 on the tape. The process was continued around the circle until the entire inner circumference of the circle was masked.
The object of the test was to apply the tape as closely as possible to the inside circumference of the 30 circle, maintaining a smooth circle design without tearing the tape edge. A break in the circle of tape indicated that the tape was less conformable than required. Four trials were run on each tape. If more than one of the four trials resulted in a break, the 35 tape was judged to be nonconformable. The results of WO95/21899 21 82 4 9 7 PCT~S95/00271 this test, as well as those for tensile, elongation and surface roughness, are given in Table 5.
.~ :
o O ~ o o o E N r~ N
O 1` ~
O ~ I O
. .
--OOOOOO o O
U~ ~ o ~ ~ o ~ ~r N ~r ~D
o m .~ r N 0 u a~ o '~
a\ ~ ~ â N ~ I Il. I~ 'I
R 1 _ --. ~ N N N o~ o~ ~
~1 ,~ 'I ~ 0 0 a ~ D ~ u ~ r ~ -- ~ o o ---- ~ ~ - c:
o a ~D ~ O O ~ u, O
_ ~
~ ~ ~ c z t) z t~ z ~ zo : - z 0 ~ ~ o _ U~ ~D ~
3 z E- X ~ X
-woss/2189s 2 1 8 2 4 g 7 PCT~S9~/00271 Results The Monadnock paper used as a backing in the tape of the present invention exhibited excellent tensile and elongation and provided a conformable tape while 5 possessing the thin caliper and surface smoothness characteristic of a flatback.
The fine creped 28 pound per ream (46 g/m2) backing from Thilmany had excellent surface smoothness and caliper, but the elongation and tensile were too low 10 for use in many masking applications. The higher basis weight fine creped Thilmany paper showed significant improvement in tensile, elongation and conformability, but the higher weight paper costs more and is thicker and stiffer, giving a boardier feel to tape made from the paper.
Backing KC S-46604 exhibited excellent tensile and elongation, but the caliper and surface roughness were higher than the other paper backings. Backing KC 6750 CE showed extremely good tensile, but low 20 elongation and poor conformability so that it could not be used for many masking applications. The glazed flatback paper from Potsdam had poor tensile as well as low elongation and poor conformability.
Only the tape of the present invention provides a 25 thin, conformable tape having a smooth surface and good physical properties (tensile and elongation), wherein no mechanical means has been applied to the backing.
Claims (19)
1. An adhesive sheet, comprising:
(a) a non-creped flatback paper backing comprising cellulosic fibers and an elastomeric saturant and having an elongation at break greater than 8%; and (b) an adhesive coating on at least a portion of at least one major surface of said backing, wherein said backing has not been subjected to any mechanical means to improve extensibility of conformability.
(a) a non-creped flatback paper backing comprising cellulosic fibers and an elastomeric saturant and having an elongation at break greater than 8%; and (b) an adhesive coating on at least a portion of at least one major surface of said backing, wherein said backing has not been subjected to any mechanical means to improve extensibility of conformability.
2. The sheet of claim 1 wherein the Tg of said saturant is less than -30°C.
3. The sheet of claim 1 wherein a Tg of said saturant is less than -45°C.
4. The sheet of claim 1 wherein the average surface roughness of said backing is less than about 7µm.
5. The sheet of claim 1 wherein said saturant is a latex acrylic saturant
6. The sheet of claim 1 wherein said adhesive is selected from the group consisting of polyacrylate; polyvinyl ether; polychloroprene; butyl rubber;
butadiene-acrylonitrile polymer; thermoplastic elastomer; block copolymer; poly-alpha-olefin; amorphous polyolefin; silicone; ethylene-containing copolymer;
polyurethane; polyamide; epoxy; polyvinylpyrrolidone and vinylpyrrolidone copolymer; polyesters; and mixtures of the above.
butadiene-acrylonitrile polymer; thermoplastic elastomer; block copolymer; poly-alpha-olefin; amorphous polyolefin; silicone; ethylene-containing copolymer;
polyurethane; polyamide; epoxy; polyvinylpyrrolidone and vinylpyrrolidone copolymer; polyesters; and mixtures of the above.
7. The sheet of claim 1 wherein said paper backing further comprises a barrier layer on at least one major surface.
8. The sheet of claim 1 further comprising a release coating on said paper backing opposite said adhesive coating.
9. The sheet of claim 1 wherein said adhesive coating is a pressure sensitive adhesive.
10. The sheet of claim 1 wherein said paper backing consists essentially of cellulosic fibers.
11. The sheet of claim 1 wherein said paper backing has an elongation at break of at least 10%.
12. The sheet of claim 10 wherein said paper backing has an elongation at break of at least 12%.
13. The sheet of claim 9 having an elongation at break greater than 8%.
14. The sheet of claim 9 having an elongation at break of at least 10%.
15. The sheet of claim 9 having an elongation at break of at least 12%
16. A method of masking a workpiece surface to facilitate painting a first area of the surface, said method comprising applying an adhesive sheet accordingto claim 1 to a second area of the surface.
17. A die-cut masking assembly comprising:
(a) at least one sheet of a non-creped flatback paper backing of a predetermined design or configuration wherein said paper backing comprises cellulosic fibers and an elastomeric saturant and has an elongation at break greater than 8%.
(b) an adhesive coating on at least a portion of at least one major surface of said paper backing, and (c) a release liner to which the adhesive composition is releasably adhered, wherein said backing has not been subjected to any mechanical means to generate extensibility
(a) at least one sheet of a non-creped flatback paper backing of a predetermined design or configuration wherein said paper backing comprises cellulosic fibers and an elastomeric saturant and has an elongation at break greater than 8%.
(b) an adhesive coating on at least a portion of at least one major surface of said paper backing, and (c) a release liner to which the adhesive composition is releasably adhered, wherein said backing has not been subjected to any mechanical means to generate extensibility
18. A method of masking a workpiece surface to facilitate painting a first area of said surface, said method comprising applying a die-cut masking assemblyaccording to claim 17 to a second area of said surface.
19. A method of making an adhesive tape comprising coating an adhesive onto at least a portion of at least one side of a non-creped flatback paper backing containing an elastomeric saturant and having an elongation at break greater than 8%, wherein no mechanical means is used to generate extensibility in the backing.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/195,873 US5496601A (en) | 1994-02-14 | 1994-02-14 | Extensible flatback adhesive sheet |
US08/195873 | 1994-02-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2182497A1 true CA2182497A1 (en) | 1995-08-17 |
Family
ID=22723170
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002182497A Abandoned CA2182497A1 (en) | 1994-02-14 | 1995-01-09 | Extensible flatback adhesive sheet |
Country Status (10)
Country | Link |
---|---|
US (1) | US5496601A (en) |
EP (1) | EP0745110A1 (en) |
JP (1) | JPH09508933A (en) |
KR (1) | KR970701245A (en) |
CN (1) | CN1140463A (en) |
AU (1) | AU1600595A (en) |
BR (1) | BR9506774A (en) |
CA (1) | CA2182497A1 (en) |
MX (1) | MX9603301A (en) |
WO (1) | WO1995021899A1 (en) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
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US6902786B2 (en) * | 1996-01-04 | 2005-06-07 | Nichiban Company, Limited | Pressure-sensitive adhesive compositions for surface-protecting films |
DE59702972D1 (en) * | 1997-01-07 | 2001-03-08 | Beiersdorf Ag | Self-adhesive masking tape |
US5935664A (en) * | 1997-10-22 | 1999-08-10 | Westvaco Corporation | Packaging material having good moisture barrier |
US6124032A (en) * | 1998-01-15 | 2000-09-26 | Bloch; Gilbert | Pressure sensitive heat activated filmic adhesive tape |
JP4486174B2 (en) * | 1999-01-14 | 2010-06-23 | リンテック株式会社 | Thermal adhesive sheet for thermal transfer printing |
WO2000056829A1 (en) * | 1999-03-19 | 2000-09-28 | H.B. Fuller Licensing & Financing, Inc. | Method for the preparation of non-blocking adhesive coated substrates and cold seal bonded laminates therefrom |
DE19960467A1 (en) * | 1999-12-15 | 2001-09-20 | Beiersdorf Ag | Adhesive tape with a thermally curable carrier for masking a KTL primer |
US6455153B1 (en) * | 2000-01-05 | 2002-09-24 | Basf Ag | Release coating for tapes |
DE10120148A1 (en) * | 2001-04-25 | 2003-02-27 | Tesa Ag | Stretchable masking tape |
US6733878B2 (en) * | 2001-12-12 | 2004-05-11 | Xerox Corporation | Thermally actuated foil-less binder tape for books |
DE10235021A1 (en) * | 2002-07-31 | 2004-02-19 | Nordenia Deutschland Gronau Gmbh | Self-adhesive surface protection film, especially for covering painted and high-gloss aluminum or stainless steel sheets |
US7195686B2 (en) | 2002-11-12 | 2007-03-27 | Masonite Corporation | Method of manufacturing a decorative substrate and decorative substrate produced thereby |
US8133353B2 (en) * | 2005-03-15 | 2012-03-13 | Wausau Paper Corp. | Creped paper product |
JP5546894B2 (en) * | 2010-02-19 | 2014-07-09 | Kj特殊紙株式会社 | Impregnated coating type washi tape base material |
US20120028524A1 (en) * | 2010-08-02 | 2012-02-02 | 3M Innovative Properties Company | Duct tape with foam film backing layer |
DE102012206648A1 (en) * | 2012-04-23 | 2013-10-24 | Tesa Se | Masking tape |
CN103509483B (en) * | 2013-09-18 | 2014-12-10 | 江门市蓬江区盈通塑胶制品有限公司 | Heat-seal adhesive tape for chemical protective clothing and production method thereof |
JP6713735B2 (en) * | 2015-07-09 | 2020-06-24 | 積水化学工業株式会社 | Masking tape |
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US2214006A (en) * | 1934-05-14 | 1940-09-10 | Kendall & Co | Method of making creped pressuresensitive adhesive material |
US2410078A (en) * | 1940-08-03 | 1946-10-29 | Minnesota Mining & Mfg | Unified fibrous fabric |
BE516549A (en) * | 1952-06-11 | |||
NL235287A (en) * | 1958-01-20 | |||
FR1150746A (en) * | 1959-02-24 | 1958-01-17 | Henri Pouyet Ets | Improvement in connection boxes for electrical pipes, more specifically for field cables |
US3104197A (en) * | 1959-06-29 | 1963-09-17 | Crown Zellerbach Corp | Extensible paper and the process of producing the same |
US3329556A (en) * | 1963-10-23 | 1967-07-04 | Clupak Inc | Non-woven fabric and method of mechanically working same |
US3359156A (en) * | 1967-02-24 | 1967-12-19 | Clupak Inc | Angle bar compactor for producing isotropic extensibility in a web |
US3503495A (en) * | 1968-11-29 | 1970-03-31 | Minnesota Mining & Mfg | Masking tape |
US3630837A (en) * | 1969-02-17 | 1971-12-28 | Clupak Inc | Compacting apparatus for fibrous webs |
US3677788A (en) * | 1970-02-03 | 1972-07-18 | Johnson & Johnson | Adhesive tape |
DE3015733C2 (en) * | 1980-04-24 | 1982-07-01 | Beiersdorf Ag, 2000 Hamburg | Process for the production of impregnated smooth or creped papers in one operation on the paper machine and their use as carrier material for pressure-sensitive adhesive layers |
US4329394A (en) * | 1980-09-09 | 1982-05-11 | Crown Zellerbach Corporation | Surface-coated, unsize-pressed cellulosic sheet and method for making same |
US4551199A (en) * | 1982-07-01 | 1985-11-05 | Crown Zellerbach Corporation | Apparatus and process for treating web material |
US4637859A (en) * | 1983-08-23 | 1987-01-20 | The Procter & Gamble Company | Tissue paper |
US4849278A (en) * | 1985-08-27 | 1989-07-18 | Kimberly-Clark Corporation | Flexible, durable, stretchable paper base web |
US4834838A (en) * | 1987-02-20 | 1989-05-30 | James River Corporation | Fibrous tape base material |
DE3835507A1 (en) * | 1988-10-19 | 1990-04-26 | Beiersdorf Ag | PAPIERKLEBEBAENDER |
US5209973A (en) * | 1988-10-19 | 1993-05-11 | Beiersdorf Aktiengesellschaft | Adhesive paper tapes |
JP2589357B2 (en) * | 1988-12-02 | 1997-03-12 | 日東電工株式会社 | Porous substrate and adhesive tape |
-
1994
- 1994-02-14 US US08/195,873 patent/US5496601A/en not_active Expired - Fee Related
-
1995
- 1995-01-09 MX MX9603301A patent/MX9603301A/en not_active Application Discontinuation
- 1995-01-09 WO PCT/US1995/000271 patent/WO1995021899A1/en not_active Application Discontinuation
- 1995-01-09 CN CN95191583A patent/CN1140463A/en active Pending
- 1995-01-09 KR KR1019960704393A patent/KR970701245A/en not_active Application Discontinuation
- 1995-01-09 AU AU16005/95A patent/AU1600595A/en not_active Abandoned
- 1995-01-09 CA CA002182497A patent/CA2182497A1/en not_active Abandoned
- 1995-01-09 JP JP7521208A patent/JPH09508933A/en active Pending
- 1995-01-09 EP EP95908011A patent/EP0745110A1/en not_active Withdrawn
- 1995-01-09 BR BR9506774A patent/BR9506774A/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
WO1995021899A1 (en) | 1995-08-17 |
BR9506774A (en) | 1997-10-14 |
KR970701245A (en) | 1997-03-17 |
MX9603301A (en) | 1997-02-28 |
JPH09508933A (en) | 1997-09-09 |
EP0745110A1 (en) | 1996-12-04 |
AU1600595A (en) | 1995-08-29 |
US5496601A (en) | 1996-03-05 |
CN1140463A (en) | 1997-01-15 |
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Legal Events
Date | Code | Title | Description |
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FZDE | Discontinued |