EVANSVILLE DIVISION
Plaintiff, )1'1',
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Plaintiff Berry Plastics Corporation, by and through its attorneys, for its Complaint
Defendant's U.S. Patent No. 7,476,416 is invalid and unenforceable under the patent laws of the
PARTIES
the laws of the State of Delaware, having its principal place of business at 101 Oakley Street,
Evansville, Indiana 47710. Except where otherwise noted, Berry Plastics Corporation is referred
under the laws of the State of Delaware, having its principal place of business at 3647 Cortez
Road West, Bradenton, Florida 34210. Except where otherwise noted, Intertape Polymer
Case 3:10-cv-00076-RLY-WGH Document 1 Filed 05/13/10 Page 2 of 10
4. This is an action for a declaratory judgment pursuant to 28 U.S.C. § 2201, for the
purpose of determining a case of actual controversy between the parties, as hereinafter more
fully appears. Jurisdiction is proper pursuant to 28 U.S.C. §§ 1331, 1338(a), and 2201. Venue is
BACKGROUND
5. Intertape is the listed assignee of U.S. Pat. No. 7,476,416 (the '''416 patent"),
of products including plastic packaging, thermoformed products, flexible films, tapes (including
8. Intertape, through its attorneys, sent a notice letter dated November 12, 2009
(hereinafter "the Letter") to Berry Plastics asserting ownership of U.S. Pat. No. 7,476,416 and
US20080058483, and US20090048407. A copy of the Letter is attached hereto as Exhibit A. The
Letter required Berry Plastics to take actions to avoid infringing Intertape's patent rights. The
Letter also requested a visit by Intertape to Berry Plastics' plant prior to commercial production
to ensure Intertape's patent rights are not violated. The '416 patent claims, inter alia, a process
for preparing an adhesive including a step whereby primary raw materials are mixed in a
compounding section of a planetary roller extruder with at least one spindle that is a double
9. Berry Plastics has taken substantial steps in meaningful preparation for the
manufacture and sale of adhesive tapes including substantial capital investment at one of its
10. Berry Plastics has purchased from Entex Rust & Mitschke GmbH (hereinafter
"Entex") a planetary roller extruder having a double transversal mixing spindle with back cut
helical flights for the purpose of manufacturing and selling adhesive for tapes.
11. The planetary roller extruder that Berry Plastics purchased from Entex has been
installed in Berry Plastics' Franklin, Kentucky facility and is currently capable of producing
12. Since at least May 3, 2010, Berry Plastics has been using the planetary roller
extruder purchased from Entex to test and make adhesive for tapes.
13. Berry Plastics intends to be manufacturing and offering for sale tapes made with
adhesive using the planetary roller extruder purchased from Entex by June 1,2010.
14. By letter to Intertape's counsel dated January 22,2010, Berry Plastics requested a
covenant not to sue from Intertape with respect to any use of the Entex planetary roller extruder
and any product made using that machinery. True and correct copies of that letter and the
requested covenant not to sue are attached as Exhibits B and C. Intertape has advised through its
counsel that it will not provide the requested covenant not to sue. Its counsel responded to
Exhibits Band C with a letter dated March 4, 2010 stating that they "believe strongly that our
client's patent is both valid and enforceable" and stating Intertape was "willing to resolve this
matter by licensing Berry's production of duct tape under the '416 patent." A true and correct
COUNT 1- UNENFORCEABILITY
15. Plaintiff Berry Plastics incorporates each of the preceding paragraphs 1-14 as if
16. Entex was an exhibitor at the National Plastics Expo, June 2003, Chicago, IL.
planetary extruders with double transversal mixing spindles with back cut helical flights at the
Expo 2003. The brochures indicated that the planetary extruder having double transversal mixing
spindles with back cut helical flights could be used to extrude rubber, a non-thermoplastic
18. Two employees of Intertape, Mr. David Kovach and Mr. Thomas Lombardo, both
named inventors on the' 416 patent, were present at the Expo 2003.
19. Mr. Kovach and Mr. Thomas Lombardo visited Entex's exhibitor booth, where
brochures describing the planetary extruder having double transversal mixing spindles with back
cut helical flights were provided to them. A true and correct copy of the Entex brochure is
materials to form adhesive was explained to Mr. Kovach and Mr. Lombardo by Entex personnel
21. On November 24, 2003, Intertape, through its counsel Mark P. Levy at Thomson
Hine LLP, filed a provisional patent application titled "Process for preparing adhesive using
planetary extruder" that was assigned U.S. Ser. No. 60/524,505 (herein after "the Provisional
Application"). A true and correct copy of the Provisional Application is attached hereto as
Exhibit F.
22. Figure 1 of the Provisional Application is identical to the image of the double
transversal mixing spindle with back cut helical flights of the Entex brochure that was provided
to Mr. Kovach and Mr. Lombardo ofIntertape by Entex at the Expo 2003.
23. The Provisional Application lists John Kinch Tynan, Jr., Richard Walter St.
24. Intertape and one or more of the listed inventors John Kinch Tynan, Jr., Richard
Walter St. Coeur, David Michael Kovach, and Thomas Lombardo, had knowledge of the Entex
brochure that was publicly displayed at the Expo 2003 during the preparation and filing of the
"Process for preparing adhesive using planetary extruder." The non-provisional application was
assigned U.S. Ser. No. 10/997,827 (hereinafter "the '827 application"). The '827 application
26. The '827 application lists John Kinch Tynan, Jr., Richard Walter St. Coeur, David
27. On April 14, 2005 applicants filed executed declarations from the listed inventors
acknowledging their duty to disclose information that is material to patentability and their
28. One or more of the listed inventors John Kinch Tynan, Jr., Richard Walter St.
Coeur, David Michael Kovach, and Thomas Lombardo and/or their counsel had knowledge of
Figure 1 of the Provisional Application, which is identical to the image of the double transversal
mixing spindle with back cut helical flights of the Entex brochure provided to inventors Mr.
David Kovach and Mr. Tom Lombardo by Entex at the Expo 2003.
29. Intertape prosecuted the '827 application before the United States Patent &
Trademark Office ("USPTO") and the '827 application issued as the '416 patent.
30. Intertape filed five separate Information Disclosure Statements on August 22,
2005; September 16, 2005; January 13, 2006; May 9, 2007; and October 4, 2007 during the
31. Entex's public presentation of the planetary extruder for use with non-
thermoplastic materials and the Entex brochure provided to Intertape at the Expo 2003 were
material to the patentability of one or more claims of the '416 patent, because they teach and/or
render obvious the claimed invention relating to the use of a planetary extruder having double
transversal mixing spindles with back cut helical flights to process non-thermoplastic material to
form an adhesive, and the examiner would have relied on this information to reject the presently
patented claims.
32. The listed inventors of the '827 application and/or the prosecuting counsel did not
disclose the material information regarding Entex's public presentation of the extruder for use
with non-thermoplastic material to form an adhesive and the Entex brochure provided at the
Expo 2003 in any of the Information Disclosure Statements filed by Intertape, and did not
apprise the examiner of the material information for determining patentability of the then
pending claims.
33. The '416 patent specification states that double transversal spindles are
commercially available from Entex. Col. 4, lines 50-2 of the '416 patent. The listed inventors
John Kinch Tynan, Jr., Richard Walter St. Coeur, David Michael Kovach, and Thomas
Lombardo and/or the counsel of record had knowledge of the statement with respect to Entex in
the specification of the '416 patent, but failed to disclose the information in an information
34. The listed inventors of the '416 patent and/or the prosecuting counsel
planetary extruder for use with non-thermoplastic materials to form an adhesive and the Entex
brochure at the Expo 2003, which were prior to the earliest claimed priority date of the '416
patent.
35. The applicants committed inequitable conduct before the USPTO during the
prosecution of the' 416 patent by intentionally failing to disclose material information regarding
Expo 2003 to the USPTO and the information provided by Entex relating to processing of non
36. Prior to the filing date of the priority Provisional Application of November 24,
2003, Entex recommended to Intertape the use of a planetary extruder having double transversal
mixing spindles with back cut helical flights for processing non-thermoplastic materials to form
an adhesive. Entex also provided Intertape with documents illustrating the planetary extruder
having double transversal mixing spindles with back cut helical flights and provided photographs
of the same. Intertape was aware that the claimed invention of the '416 patent was originally
provided by Entex to Intertape prior to the filing date of the Provisional Application.
37. Intertape intentionally failed to disclose to the USPTO the material information
that Entex provided to Intertape regarding the claimed use of a planetary extruder having double
transversal mixing spindles with back cut helical flights for processing a non-thermoplastic
conduct to obtain the '416 patent by intentionally failing to disclose material information that
showed that Intertape did not invent the claimed invention of the '416 patent and that Entex
39. The '416 patent and any subsequent related applications are unenforceable
because Intertape committed inequitable conduct by listing Intertape personnel as inventors who
are not the actual inventors and excluded Entex personnel as inventors with deceptive intent to
Intertape is permitted to assert patent rights based on the unenforceable'416 patent or any of its
subsequent related patent applications and thereby prevent Berry Plastics from manufacturing
and selling in the immediate future adhesive for tapes using the Entex planetary roller extruder
41. Berry Plastics incorporates each of the preceding paragraphs 1-40 as if fully set
forth herein.
42. The United States Patent No. 7,476,416 ("the '416 patent"), entitled "Process for
preparing adhesive using planetary extruder" lists 2 independent claims and 32 dependent
claims. A true and correct copy of the'416 patent is attached hereto as Exhibit G.
43. One or more claims of the' 416 patent are invalid for failing to satisfy the written
description and/or definiteness and/or enablement and/or best mode requirements of 35 U.S.C. §
112.
44. One or more claims of the' 416 patent are invalid as being anticipated under 35
U.S.C. § 102.
45. One or more claims of the '416 patent are invalid under 35 U.S.C. § 102(±)
because applicants themselves did not invent the subject matter sought to be patented and
46. One or more claims of the ' 416 patent are invalid as being invalid under 35
U.S.C. § 101.
47. One or more claims of the '416 patent are invalid under 35 U.S.c. § 256 because
the applicants, with deceptive intent, omitted inventors, and named persons who are not
inventors.
48. One or more claims of the '416 patent are invalid for being obvious under 35
U.S.c. § 103.
Intertape is permitted to enforce the '416 patent or any of its subsequent related patent
applications and thereby prevent Berry Plastics from manufacturing and selling in the immediate
future adhesive for tapes using the planetary roller extruder now installed in its Franklin,
Kentucky plant.
alternatively:
(a) A judgment ordering that the' 416 patent and any of its subsequent related
patent applications are unenforceable due to inequitable conduct at the patent office;
(b) A judgment that one or more of Entex personnel are the sole inventors of
(c) A judgment that one or more of Entex personnel are co-inventors of the
9
Case 3:10-cv-00076-RLY-WGH Document 1 Filed 05/13/10 Page 10 of 10
'416 patent;
(d) A judgment that the' 416 patent is invalid under 35 U. S.C §§ 101, 102, 103
and/or 112;
(e) A declaration that Berry Plastics may use the planetary roller extruder in
its Franklin, Kentucky plant free and clear of the '416 patent and any of its subsequent related
patent applications;
(h) Such further and other relief as this Court may deem just and proper.
Respectfully submitted,
Daniel P. Albers
Jonathan P. Froemel
Mark 1. Nahnsen
BARNES & THORNBURG LLP
One North Wacker Dr., Suite 4400
Chicago, Illinois 60606
Telephone: (312) 357-1313
Facsimile: (312) 759-5646
CHDSO] 599062v]
10
EXHIBIT A
We represent Intertape Polymer Group. Our client is the owner of the following U.S. patent and
published patent applications in the United States:
Our client recently read a press release dated September 30, 2009 in which Berry Plastics announced that
it is making capital improvements, in the amount of $20 Million. to its facility in Franklin, Kentucky,
Intertape is aware that Berry manufactures a number of tape products at its Franklin facility, including
duct tape.
The purpose of this letter is to place Berry Plastics Corporation On notice of the foregoing patent and
published applications so that Berry Plastics can take steps to avoid infringing them. Intertape will
revisit this matter with Berry periodically in the future, particularly as Intertape's pending applications
issue. Additionally, before Berry's new facilities begin commercial production, Intertape will need
assur-ances that Berry's processes do not infringe. At that time, Intertape will also want to make
arrangements for its counsel, and possibly an independent coating engineer, to visit the Franklin facility
to verify that lntertape's patented technology is not being used,
THOMPSO
__N:.:.- _
-mNE-
Mr. Tom Salmon
November 12,2009
Page 2
We appreciate your cooperation in this regard. We can assure you that Intertape intends to vigorously
enforce its rights in its current and future patents.
Case 3:10-cv-00076-RLY-WGH Document 1-2 Filed 05/13/10 Page 1 of 4
EXHIBIT B
Mark. P. Levy
Thompson Hine LLP
2000 Courthouse·Plaza, N.E.
lOW. Second Street
Dayton, Ohio 45402
In investigating the matters raised in your letter, we understand that Intertape employees,
including Mr. David Kovach and Mr. Thomas Lombardo, attended the National Plastics Expo in
June 2003 (hereinafter "Expo") in Chicago, where Entex Rust & Mitschke GmbH (hereinafter
"Entex") was an exhibitor. At the Expo, Entex gave a presentation on a planetary extruder
having double transversal mixing spindles with back cut helical flights (the ''Noppenspindel'') for
use with non-thermoplastic materials to form adhesive and distributed brochures to Intertape
describing the same at the Expo. The brochures indicate that such equipment is used with rubber,
a non-thermoplastic materiaL
In addition, Mr. Kovach and Mr. Lombardo from Intertape visited Entex's exhibitor
booth, where brochures describing the Noppenspindel was displayed. We also understand that
Mr. Kovach and Mr. Lombardo were lectured by Entex regarding the use of the planetary
extruder with the Noppenspindel for use with non-thermoplastic materials to form adhesive.
Intertape had knowledge of Entex's public presentation on the planetary extruder using the
Noppenspindel for non-thermoplastic materials. This is the same method that Intertape now
claims it invented as claimed. in the '416 patent. Despite having knowledge of the public display
MarkP. Levy
Page 2
and other information provided by Entex in June 2003, Intertape filed a provisional application
within five months, in November 2003, using a photocopy of an image of the Noppenspindel
provided by Entex and shown in their brochure, as Figure 1 in the provisional application.
Intertape also filed and prosecuted the corresponding non-provisional application (U.S. Ser. No.
10/997,827) that resulted in the '416 patent. Even though Intertape had knowledge ofEntex's
prior invention, none of the information disclosure statements filed contained any reference to
the 2003 Expo or Entex's public demonstration or publication prior to the filing date of the
provisional application.
In addition, Intertape argued against the alleged non-obviousness of the claimed methods
by stating that a skilled artisan would not consider adding a double transversal planetary spindle
to a planetary extruder for processing non-thermoplastic materials. Yet, the Entex brochure, the
public presentation, and information provided to Mr. Kovack and Mr. Lombardo showed that
non-thermoplastic material (e.g., rubber) was being used with planetary extruders having double
transversal mixing spindles with back cut helical flights by Entex. Despite having knowledge of
the Entex Noppenspindel at the 2003 Expo and brochures describing the same, these false
statements regarding non-obviousness were made by Intertape through its counsel to the USPTO.
Intertape failed to disclose to the USPTa material information regarding Entex's public
presentation of the planetary extruder having the Noppenspindel and the brochures describing the
same that occurred prior to the filing date of the provisional application. Intertape also made
false statements regarding non-obviousness before the USPTa to obtain the '416 patent. The
failure to disclose the material information regarding patentability to the USPTO and false
statements made regarding prior art render the'416 patent and all of its related applications
invalid and unenforceable. Despite having this knowledge, Intertape now makes frivolous
allegations of infringement that in turn, have needlessly increased the commercial production
and litigation costs for Berry Plastics to defend its right to manufacture.
Given the conduct of Intertape, Berry Plastics has filed and we enclose a declaratory
judgment complaint to invalidate and render unenforceable the '416 patent. Please understand
that Berry Plastics will aggressively move for reimbursement ofits litigation expenses, including
attorney's fees, and costs to defend against Intertape's baseless allegations. We have not yet
served the complaint on Intertape, but we will do so unless we can bring this matter to an
expeditious resolution.
In order to resolve this matter, we demand that Intertape agree to a covenant not to sue
Berry Plastics and its customers based on the '416 patent and any related applications or future
BARNES&1HORNBURG llP
Case 3:10-cv-00076-RLY-WGH Document 1-2 Filed 05/13/10 Page 4 of 4
MarkP. Levy
Page 3
related applications, for the use of any machinery Berry Plastics acquires from Entex relating to
extrusion of non- thermoplastic material and any product resulting from the use of such
machinery. A proposed covenant not to sue is enclosed. IfIntertape agrees to such covenant,
Berry Plastics will dismiss its complaint without prejudice. Please advise us within the next two
weeks, before February 5th with respect to Intertape's response regarding the covenant not to
sue.
~-
~;(lber
CHDSOI 580640"I
BARNES&1HORNBURG UP
Case 3:10-cv-00076-RLY-WGH Document 1-3 Filed 05/13/10 Page 1 of 5
EXHIBIT C
This Covenant Not to Sue ("Agreement") is made and effective as of the L - ) day of
a corporation organized and existing under the laws ofthe State of Delaware, having its principal
place ofbusiness at 3647 Cortez Road West, Bradenton, Florida 34210, and Berry Plastics
Corporation (hereinafter "BERRY PLASTICS"), a corporation organized and existing under the
laws of the State of Delaware, having its principal place of business at 101 Oakley Street,
Whereas INTERTAPE is the listed assignee of issued U.S. Pat. No. 7,476,416 and has
Whereas BERRY PLASTICS is planning to manufacture, sell, distribute, and offer to sell
a variety of tapes including adhesive tapes having an adhesive processed by a planetary extruder
having double transversal mixing spindles with back cut helical flights with machinery
Whereas INTERTAPE has sent a letter to BERRY PLASTICS putting them on notice of
their rights in the Intertape Intellectual Property including U.S. Pat. No. 7,476,416;
Whereas BERRY PLASTICS has filed a declaratory judgment action (Civil Action Case
No. lO-cv-OOO 14) in the District Court, Southern District ofIndiana (hereinafter "DJ Action") to
inter alia, invalidate and render unenforceable U.S. Pat. No. 7,476,416; and
Case 3:10-cv-00076-RLY-WGH Document 1-3 Filed 05/13/10 Page 3 of 5
Whereas, the parties desire to settle and resolve all controversies and claims relating to
The Intertape Intellectual Property and the DJ Action lawsuit to avoid the burden and expense of
further litigation;
1. This Agreement is entered into solely for the purpose of avoiding the burden and
expense of further litigation and neither it nor any negotiations leading up to it is intended to be,
PLASTICS.
subsidiaries, affiliates, any of the foregoing's respective past, present or future officers, directors,
distributors, customers, users or any other parties for the importation, export, manufacture, use,
sale, or offer for sale by BERRY PLASTICS or its subsidiaries or affiliates ofEntex planetary
extruders having double transversal mixing spindles with back cut helical flights and products
manufactured using the same or a substantially similar process or equipment, including but not
limited to any manufacture using machines or know-how provided by Entex for infringement or
on any other theory including direct or indirect infringement, inducement or contribution, under
Property, as well as any patents or patent applications claiming priority therefrom, together with
equivalents thereof, to make, have made, import, export, use, sell, and offer for sale. BERRY
PLASTICS' rights hereunder shall be transferable by operation oflaw or in connection with the
sale of any relevant portion of its business or substantially all of the assets of such portion of its
business.
within ten (l0) business days of the effective date of this Agreement.
5. This Agreement shall benefit and be binding upon the parties, successors and their
respective assigns. INTERTAPE acknowledges and agrees that this covenant not to sue is
extended on behalf of (and extends to) any and all of its affiliates, subsidiaries, and parents and
runs with the title of the Intertape Intellectual Property for any activity, inducement, contribution,
Indiana Law, and the parties agree that the sole venue for enforcement of this Agreement shall be
the United States District Court for the Southern District of Indiana.
7. This Agreement supersedes and abrogates all former verbal or written agreements
between the parties hereto related to the subject matter hereof, and is the only agreement in
existence between the parties and is not subject to change except by mutual agreement, in writing,
8. The parties warrant and represent that each has been represented by counsel of
their choice in connection with the review, approval and execution of this Agreement; that each
has shown this Agreement to its respective attorney who has explained it and advised it that it is
a legally binding contract; that each has read and understood this Agreement; and that each
3
Case 3:10-cv-00076-RLY-WGH Document 1-3 Filed 05/13/10 Page 5 of 5
which is not specifically provided in this Agreement has been made by any party to this
Agreement; that this Agreement contains the entire agreement among the parties; and that the
terms of this Agreement cannot be modified except in writing signed by all of the parties.
10. This Agreement maybe executed in counterparts each of which shall constitute an
original.
By: _
Date
Name: _
Title:
-------------
By:
Date
Name:
-------------
Title: - - - - - - - - - - - - -
CHDSOl580857vl
EXHIBIT D
Stephen J. Butler
(513) 352-6587
Steve.Butler@ThompsonHine.com
March 4,2010
Gentlemen:
We have thoroughly investigated the what seems to be the linchpin of your case,
which is the supposed interaction between representatives of Entex and Intertape Polymer
Corporation at the Chicago trade show in June, 2003. We do not know the source of your beliefs
about what happened at that show, but you have the facts wrong. Furthermore, the Entex
document that you attached as an exhibit to the complaint does not teach the invention claimed in
Intertape's '416 patent. We continue to believe strongly that our client's patent is both valid and
enforceable. Our analysis is based in part on Hess v, Advanced Cardiovascular Systems, Inc.,
106 F.3d 976, as well as the heavy burden of proof that your client must meet to prevail.
Stephen J. Butler
SJB/SEB
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Case 3:10-cv-00076-RLY-WGH Document 1-5 Filed 05/13/10 Page 3 of 19
Case 3:10-cv-00076-RLY-WGH Document 1-5 Filed 05/13/10 Page 4 of 19
ENIEX
Speech D1K '03 Seite 1
I would like to thank you very much in the name of ENTEX for giving me the
opportunity to present to you the construction and mode of action of the planetary
roller extruder.
First of all I want to introduce the ENTEX company. ENTEX has been founded in
1986 and has today 88 employees. The name ENTEX stands for "ENTwicklung
EXtrusion" = development extrusion. Right from the beginning, we at ENTEX
identified ourselves with this name which is proved by more than 30 patents and
patented designs.
Our main product is the planetary roller extruder. More than 40 years ago Mr.
Wittrock of Messrs. Chemische Werke Hills AG has invented the planetary roller
extruder. Since that time this system is an integral part, especially regarding the
compounding of PVC, which - as we all know - is a thermal sensitive material so
that already here the characteristic of this system is demonstrated. There is no
other system existing which allows not nearly such an excellent temperature
control in the compounding process.
Besides the well-known types of plastics such as thermoplast (PVC, PP. PE,
TPU), duroplast, powder coatings, which are at present processed by means of a
planetary roller extruder, ENTEX has made a leap in an effective and economical
method of compounding elastomer masses.
Due to their special properties, as for example damping characteristics, media and
ageing resistance as well as their thermal stability, elastomers are used more and
more as insulating material, insulations, adhesives and much more in the
automotive industry, by cable makers and in many other industrial ranges.
The small cooling area and the relatively large volume of the chamber of the
internal mixer only allow a slight effect on the temperature control, which results in
a relatively long mixing period or alternately formulating compromises are made in
this area.
Case 3:10-cv-00076-RLY-WGH Document 1-5 Filed 05/13/10 Page 5 of 19
ENIEX
Speech DIK '03 Seite 2
This disadvantage regarding the temperature control and formulation does not
exist in the case of the planetary roller extruder.
Moreover, the discontinuous mixing process incurs high energy and economic
costs and must be regarded, due to the system, as requiring intensive time and
capital. In order to achieve a better process with regard to a continuously good
quality in mixing it is better to use a planetary roller extruder in view of process
technique and economy.
But at first some words concerning the construction of the planetary roller extruder:
The planetary roller extruder is a mixing heat exchanger with dynamic discharging
effect. The planetary roller part is the constructive and dominating zone with
regard to the process technique. The planetary roller part is constructed similar to
a planetary gear (Fig. 1). The drive is carried out via the central spindle which, in
0
turn, distributes the torque to the planets. These roll off in the 45 helical toothed
cylinder.
Due to the helical gearing of the planetary system a continuous rolling out of the
material is built up at simultaneous discharge in direction outlet of the roller part.
This guarantees the best self-cleaning effect of all compounding extruders. When
using an open stop ring practically the whole material - except few material
residues - will be rolled out of the roller part so that e.g. very economic changes
in colour resp. formulations can be achieved.
Case 3:10-cv-00076-RLY-WGH Document 1-5 Filed 05/13/10 Page 6 of 19
Construction sizes:
Characteristics:
Due to the extremely thin wall thickness (Fig. 3) of the cylinder assembly and the
central spindle an excellent controlling of the temperatures of the contact surface
area is given. By the introduction of the pressure water heating and an improved
construction of the cooling channels which allow a product-near temperature
control thus influencing decisively the heat transmission, this system has found an
increasing acceptance.
There is no other compounding system existing which allows not nearly such an
excellent temperature control in the compounding process.
Case 3:10-cv-00076-RLY-WGH Document 1-5 Filed 05/13/10 Page 7 of 19
It will be more simple to explain this in comparison with other systems, co-kneader
or twin screw {Fig. 5}.
Fig. 4:
When you have a look at the co-kneader and the twin screw you will recognize
that these systems are systems of internal friction and that for the plasticizing they
have to be filled.
Kneading segment
Kneading housing
Screw fllte cooling passages
Heating/Cooling Heating elements
chamber
EN'EX
Speech DIK '03 Seite 5
To give you an impression of the contact surface area of a planetary roller extruder
we will look at the standard size of an extruder for calender feeding, i.e. TP-WE
250/2000-M2 (Fig. 6). On one rotation of the central spindle this extruder contacts
an area of more than 12 m2 ,
i.e. at 50 r.p.m. an area of 600 m2 . This corresponds nearly to twice the size of a
tennis court (Fig. 8).
QlUS~l!>w>"l.rtl!l
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e 1f.,O
0100
.
Walil."nl~ll.l'I:Y~ [rrunl
ENJEX
Speech DIK '03 Seite 6
0,07
0,06
0,05
0,04
0,03
0,02
0,01
°
Qmech J Q l f c h ~}Q;)b
Vergleich der Energiebll21nz verschledener AufbereitungsSY5teme (bel mutter ern Eurchsetz)
Fig. 9 shows the energy balance of different compounding systems. You will see
that the planetary roller extruder - at less drive power - offers due to its surface an
essentially larger heat exchange than the two other systems. The bottom part
shows the supplied motor energy, the upper part the heating capacity to be
possibly supplied. the outside part represents the radiation energy released by the
machine surface.
Moreover, due to the modular construction, the temperature profile and thus the
melt temperature can be controlled in a wide range, more details will follow later.
Case 3:10-cv-00076-RLY-WGH Document 1-5 Filed 05/13/10 Page 10 of 19
EN'EX
Speech DIK '03 Seite 7
Until now, the compounding in the caoutchouc industry takes place - contrary to
the planetary roller extruder - by batch-wise discontinuous mixing in the internal
mixer (Fig. 10), if necessary in several mixing stages.
cyllnder.--·..·..
Fig. 10: Drawing of a
standard internal mixer
feeding flap.~"
reeding punch
blade
---~ c001lng zcone
intermediate
:.- .. stage
, /'
stopper rod
ground floor
1011111111
The gelation process in the internal mixer is executed in a closed chamber (Fig.
11) in which two opposed rotors, equipped with kneading elements, are running.
Case 3:10-cv-00076-RLY-WGH Document 1-5 Filed 05/13/10 Page 11 of 19
ENJEX
Speech DIK '03 Seite 8
The real plasticizing parts are the kneading blades (Fig. 12). Here you have to
make a distinction between two different arrangements: the tangential (left) and
the intermeshing (right) rotors.
In the case of the conventional tangential rotors the outer rotor diameter
corresponds approx. to the distance of the axles which means that the blades are
not intermeshing and therefore can be operated with different speed (= friction).
In the case of intermeshing rotors both kneading blades must run with the same
speed. By this principle the material will be in fact (due to the higher supplied
shear energy) quicker plasticized, unfortunately, however, the thermal charge will
be higher. Remedy can be achieved by lowering of the filling grade by which,
however, the throughput is decreased as well.
This makes clear the great difference between the discontinuous processing on an
internal mixer and the continuous processing in a planetary roller extruder.
The planetary roller extruder of the construction size 250 (TP-WE 250) has per
each cylinder assembly a max. filling volume of 9,5 I (at full planet equipment) with
a heating/cooling area of more than 20.000 em", From one litre material results
therefore a static contact surface area of 2.100 ern", a value to which no internal
mixer will come up. A comparable internal mixer reaches - depending on the filling
level - 1/10 up to 1/8 of this value. We have already got to know which dimensions
the contact surface area of the planetary roller extruder can achieve during
operation (Fig. 8 - tennis court).
Moreover you will see that the wall thickness (Fig. 13) between heating-cooling
medium and material to be processed is essentially thinner and therefore more
economical in the case of a planetary roller extruder. But there is no other
possibility as the internal mixer requires - due to its high power for the kneading
process - of course a strength which such a thin wall thickness does not allow.
Case 3:10-cv-00076-RLY-WGH Document 1-5 Filed 05/13/10 Page 12 of 19
ENJEX
Speech DIK '03 Seite 9
Also with regard to the power it becomes clear that the planetary roller extruder
needs a clearly smaller amount of energy required, the already above mentioned
TP-WE 250 requires "only" a 350 kW drive. The variations of different specific
drives, e.g. 0,05 - 0,3 kW/kg for elastomers at a constant outlet enthalpy (losses in
temperature) of the material, can only be realized with a planetary roller extruder.
A further essential difference between internal mixer and the planetary roller
extruder is the feeding.
The caoutchouc balls used in the internal mixer are still today weighed out
manually and all further ingredients are adapted accordingly. The possible sources
of error in this procedure might be known.
In the planetary roller extruder exclusively caoutchouc pellets (Fig. 14) are used.
This is necessary in order to guarantee an optimal feeding of the aggregate and to
make a constant feeding possible in general.
Fig. 14: Pellets of comminuted caoutchouc balls for continuous feeding of the extruder
Case 3:10-cv-00076-RLY-WGH Document 1-5 Filed 05/13/10 Page 13 of 19
ENIEX
Speech DIK '03 Seite 10
The essential difference to the internal mixer is that the planetary roller extruder
can be fed only with pellets. Therefore, the caoutchouc balls must be comminuted
and pelletized at first.
In both cases the pelletized raw materials can be stored in silos or tanks and can
be supplied to the compounding machines via pneumatic conveyor equipment or
optionally in barrels or bags.
In the case of the internal mixer the weighing of the formulation components is
done automatically, normally, however, manually.
the feeding of the planetary roller extruder takes place by means of the continuous
dosing with gravimetric dosing units. By means of the gravimetric dosing a
computer controlled material feeding is possible. This means that also during
running production process optimizing can occur, errors in dosing can be avoided
and therefore a constant high material quality can be maintained.
As explained already above, in the case of the internal mixer the mixing process is
a discontinuous process consisting of feeding - mixing - emptying and, should the
occasion arise, the mixing takes place even in several mixing stages.
In the case of the planetary roller extruder the mixing process is a continuous,
single stage process.
After the mixing in the internal mixer, further treatment is carried out in the rolling
mill. The mixture is rolled out as a sheet, which is then cooled and coated with
parting agents. Then the sheet is dried and laid down before it is supplied to a
calender or extruder for further processing.
When using a planetary roller extruder you can give up these intermediate steps.
The compounded material will be e.g. further processed directly by means of a
gear pump or via a flat film die.
ENiEX
Speech DIK '03 Seite 11
state-of-the-a rt state-of-the-art
internal mixer planetary roller
extruder
manpower pelletizing
required weighing
persons (estimated) mixing comparable
after-treatment aggregates with a
throughput of
investment pelletizing X approx. 1.200 kg/h
required weighing X XX
x 500.000€ each mixing XX X
(estimated)
after-treatment XX X
In the following exemplary process diagram (Fig. 15) a planetary roller extruder
for example can be fed with up to seven solid components (e.g. caoutchouc,
resins, additives etc.) simultaneously, parallel and in every requested dosing.
Furthermore, this is also still possible for two liquid components (e.g. softener).
Thus, at the touch of a button, the formulation can be changed at any time or the
throughput can be adapted - without down-times, without conversion works and
thus without set-up costs.
Fig. 15: Schematic concept of a production line for the continuous compounding of elastomers
Case 3:10-cv-00076-RLY-WGH Document 1-5 Filed 05/13/10 Page 15 of 19
Development:
A pioneering progress has been the production of the heatable cylinder by means
of the spark erosion process.
Fig. 16a: Spark erosion machine Fig. 16b: Inside view with roller cylinder
The pictures (Fig. 16a-d) show the function and mode of action of the spark
erosion technology. By this technology an electrode consisting of graphite is
produced on an involute milling machine. Then this will be eroded, practically 1 : 1,
in a hardened steel cylinder. The erosion process guarantees an optimal
development of the involute with all necessary profile displacements, i.e. every
clearance modifies inevitably the involute curve.
ENiEX
Speech DIK '03 Seite 13
The advantage of this erosion process is that you can practically erode in very
steel, notwithstanding the hardness.
Today the grinding is restricted to approx. 500 mm, so that the liners should be
coupled or welded respectively.
In case liners must be coupled or welded you have to calculate with a heat
warpage. In order to avoid this heat warpage, wall thicknesses which are possible
with the erosion technique, cannot be achieved. Therefore, you will not get the
heat transfer possibilities for these extruders as per the whirling or grinding
process, which you can achieve with an eroded roller part. This means a reduction
of the process window.
The erosion technique has been a milestone in the development of the planetary
system and the outcome was to fabricate the planetary roller extruder in modular
construction.
Fig. 17: Presentation of the "modular construction" of the planetary roller extruder
By means of the equipment of the planetary spindles and the variation of the stop
ring diameter the dwell time of the melt and the pressure build-up can be varied.
Case 3:10-cv-00076-RLY-WGH Document 1-5 Filed 05/13/10 Page 17 of 19
Process affects
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ E: ... I E: ><
200
150
planetav
-'-_ _~ ---,- .__--__;_-------4-s'--plndles
I I i
7 PSP 6 PSP 5 PSP
uecenuence..Q!.ttle.m.elt.preSS.Ule._.spe.Clllc.ener.I:l{..and.meit.tem~erature.Qn.lt\e.nllmOeJ.o(.plane.~rf ..,p.lJ]di.e.L..
rs
Fig. 18 Dependence of the pressure build-up of the planetary roller extruder on the number of
planetary spindles
Fig. 18 shows the dependence of the specific power, melt temperature and
melt pressure on the number of planetary spindles. It becomes clear that with
for example 7 planetary spindles the pressure build-up in front of the
intermediate stop ring is essentially higher.
Process affects
_______.._. ~~J E: ><
luph
200 "1{j(I--~
190 'juG ..j
..~
170 HO-- :
:mo-i
planetary
'- -'--_ _--,--_ _- - , , --4,,5.;....'PlnJjleS
I I I
7 PSP 6 PSP 5 PSP
Pr.oc.e.5.s..atf.e.ctS.DJ.S1DP..flI.1Q ..d.larneter.a.ndnumber,.or.'p.lanetaclspmcllt:5.
rs
Fig. 19 shows the process effect of stop ring diameter and number of planetary spindles
The new modular system allows the variation of the process length and thus a
gentle compounding of materials which are difficult to disperse or homogenize, as
for example recycled materials, adhesives, caoutchoucs, etc.
The difference in quality between the known extruders and the planetary roller
extruders in modular construction is more than grave.
Case 3:10-cv-00076-RLY-WGH Document 1-5 Filed 05/13/10 Page 18 of 19
ENIE:X
Speech DIK '03 Seite 15
We see further developments in Fig. 20 and Fig. 21. On the one hand the (for
special applications) varied tooth geometry of the planetary spindles becomes
visible, on the other hand the construction of the separable dispersion ring is
perceptible. This is used mainly when processing liquids and very low viscous
materials.
Fig. 21: Central spindle (left) and separated dispersion ring (right)
Glimpsing ahead with regard to the possibilities of the roller mixer system I want to
present you some types of extruder (Fig. 22 - 25):
Fig. 22: Reaction roller mixer with 4 modules Fig. 23: Planetary roller extruder,
vertical construction
Case 3:10-cv-00076-RLY-WGH Document 1-5 Filed 05/13/10 Page 19 of 19
ENIEX
Speech DIK '03 Seite 16
Fig. 24: Chemical roller mixer C-WM 400/3000-M3 Fig. 25: Planetary roller extruder
TP-WE 250 with twin stuffing
device
In future, the demand for high efficient compounding extruders like the planetary
roller extruder will increase due to new developed formulations.
EN EX
Rust & Mitschke GmbH
Heinrichstr. 67
44805 Bochum
Tel.: +49 (0)234 - 891 22-0
Fax: +49 (0)234 - 891 22-99
e-mail: ~ales@E!ltex-Boc:hum.de
www.Entex-Bochum.de
Case 3:10-cv-00076-RLY-WGH Document 1-6 Filed 05/13/10 Page 1 of 12
EXHIBIT F
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PROVISIONAL APPLICATION FOR PATENT COVER SHEET
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Richard Waller
St. Coeur Marysville, Michigan
Additional inventors are being named on the 1 separatuly numbered sheet» ettscnea hereto
TITLE OF THE INVENTION (500 characters max)
PROCESS FOR PREPARING ADHESIVE USING PLANETARY EXTRUDER ~
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D Yes, the name of the U.S. Government agency and the Government contract number are:
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and foaming agents, and subsequent application to a web-form material via slot-die.
The general purpose of the invention is to provide a method for producing a self
viscosity adhesive that can be applied using a slot die through the use of 'back-cut"
Back-cut planetary spindles are spindles having openings in the flights that permit
material to pass between the wall of the barrel and the screw and slow the rate with which
material passes through the PRE. One example of a back-cut spindle is a so called
porcupine spindle. Another example is shown in Fig 1 hereto. PRE's having back-cut
of full flight and open or back-cut spindles, the rate with which material passes through
the PRE and hence the amount of mastication that is done on the material is controlled. A
PRE with all full flight spindles does less masticating than a PRE with spindles in which a
portion of the flights is open or back-cut. Conventional PRE's contain at least 3 and can
contain up to 20 spindles, depending on the diameter of the cylinder and process design.
- 1
Case 3:10-cv-00076-RLY-WGH Document 1-6 Filed 05/13/10 Page 6 of 12
In one embodiment of the invention, a PRE having a 70mm diameter cylinder having 6
spindles is used. Another factor that affects the amount of mastication is the internal
diameter of the stop ring. By narrowing the gap between the stop ring or dosing ring and
the spindle, more mastication can be performed. In one embodiment of the invention
crosslinkers, and colorants, in addition to liquid components, are fed into the
compounding sections of the PRE. Additionally, and perhaps most importantly, one
embodiment of the invention involves the feeding of solvent into the compounding
sections of the PRE via dosing rings. Another embodiment of the invention involves
coating the self-adhesive composition on a web-form material, where the coating of the
web-form material is carried out using a slot-die applicator unit. One slot die unit that is
used in one embodiment includes a spindle that trails the die lip. One example of such a
Simply stated, the disadvantage of the methods taught in the Beiersdorf patents
are: 1) Beiersdorf does not teach the effective, efficient, and controlled mastication of
non-thermoplastic elastomers, e.g. natural rubber, particularly through the use of "back
cut" planetary spindles, in combination with full-flight planetary spindles, 2) the Beiersdorf
does not teach the feeding of solid components, e.g. thermoplastic elastomers, resins,
the compounding section of the PRE, 3) the Beiersdorf process does not teach the
compounding of adhesives with solvents, and 4) the Beiersdorf process does not teach
-2
Case 3:10-cv-00076-RLY-WGH Document 1-6 Filed 05/13/10 Page 7 of 12
adhesive coating methods other than a multi-roll applicator unit. These disadvantages
combine to limit the flexibility in designing the performance properties of the finished
Specifically, the modified PRE includes a feeding section and subsequent compounding
sections. The feeding section includes a single-screw barrel section with a throat into
which solid or liquid raw materials, e.g. elastomers, resins, extenders, activators,
antidegradents, and crosslinking agents, etc, can be introduced. The single screw then
conveys these raw materials into the first compounding section. In one embodiment a
PRE having four compounding sections, i.e., four planetary roller barrel sections
separated by stop or dosing rings. Each planetary compounding section consists of a 45°
helical toothed cylinder, a 45° helical toothed main spindle and three or more (for
planetary spindles is a function of the diameter of the cylinder. The planetary spindles
can exhibit many different tooth geometries, e.g. full helical flights (Planetspindel), back
cut helical flights (Noppenspindel), or zoned helical flights (Igelspindel), etc. The number
of planetary spindles chosen and their geometries (e.g., open vs. full flight) can be
materials, e.g. liquid elastomers, molten resins, oils, solvents, etc., can be introduced into
the compounding sections via injection nozzles through the dosing ring assemblies.
Additionally, the gap between the dosing ring and the main spindle can be changed to
-3
Case 3:10-cv-00076-RLY-WGH Document 1-6 Filed 05/13/10 Page 8 of 12
vary the dynamic discharging effect of each compounding cylinder and the discharging
can be modified with twin-screw dosing units. The twin screw dosing units are typically
positioned perpendicular to the axis of the compounding sections and are typically located
near the beginning of the compounding sections directly adjacent to the dosing rings.
The twin-screw dosing units can be employed to introduce solid components, e.g.
include natural rubber, synthetic polyisoprene, styrene butadiene rubber, butyl rubber and
employed in this process are block copolymers, e.g. SIS, SBS, SEBS, and SEPS, and
any combination thereof. Typical resins include hydrocarbon resins, partially or fully
hydrogenated wood, gum, or tall oil rosins, esterified wood, gum or tall oil rosins, alpha
and beta pinene resins, and polyterpene resins. The resins can be introduced in both
solid and molten form. Typical extenders include clays, calcium carbonate, talc, and
aluminum hydrates. Typical activators include zinc oxide and magnesium oxide. Typical
Typical colorants are titanium dioxide and other various metal pigments. Typical liquid
elastomers are low molecular weight natural rubber and low molecular weight synthetic
-4
Case 3:10-cv-00076-RLY-WGH Document 1-6 Filed 05/13/10 Page 9 of 12
aliphatics such as toluene, hexane, heptane, and blends thereof. Examples of foaming
various solid raw materials into the compounding sections, 3) the introduction of solvent
into the compounding sections, and 4) the use of slot-die coating technology.
the elastomers are forced with the single-screw from the feeding section between the
dosing ring and the main spindles into the compounding sections, where it is intensively
with other solid and liquid materials, yields the potential for a greater ratio of tack to
adhesion in the finished adhesive and yields a finished adhesive with lower viscosity that
is not limited to being coated via a multiple roll applicator unit (calender). This provides
The introduction of various solid raw materials into the compounding sections has
several advantages. First, all solid materials do not have to be introduced all at once in
the feeding section of the PRE, i.e. they can be dosed in one or more of the compounding
-5
Case 3:10-cv-00076-RLY-WGH Document 1-6 Filed 05/13/10 Page 10 of 12
sections. ~rhis gives the elastomer more time to be masticated prior to the addition of
solid raw materials and increases the mixing efficiency of the PRE up to 25%. Second,
solid resin, as opposed to molten resin can be introduced into the compounding sections.
The solid resin has a viscosity that more closely resembles the elastomer, when
liquid) resin further enhances mixing efficiency, whereas molten resin tends to act as a
lubricant and retards mixing efficiency. Additionally, the solid resin has a specific heat
which affords it the ability to act as a heat sink, l.e. take heat away from the process,
thereby minimizing the temperature of the melt during the compounding process.
Conversely, molten resin increases the temperature of the melt in the compounding
process.
The introduction of solvent into the compounding sections has several advantages.
First, small amounts (e.g., typically 10 to 20% by weight but amounts up to 50% could
feasibly be used) of solvent, introduced to the adhesive through several dosing rings,
enhances mixing efficiency, i.e. maintains homogeneity, while significantly lowering the
viscosity of the finished adhesive. The solvent is readily absorbed by the adhesive
composition and the incorporation of solvent lowers the resultant homogenous adhesive's
viscosity to the point that its application to a web-form material is not restricted to a multi
roll applicator unit (calender). Rather, the lower-viscosity adhesive can now be applied to
adhesive application techniques. The subsequent liberation of the solvent from the
adhesive that has been applied to the web-form material affords the ability to effect
-6
Case 3:10-cv-00076-RLY-WGH Document 1-6 Filed 05/13/10 Page 11 of 12
numerous surface geometry profiles, i.e. degrees of foaming, in the adhesive film.
The use of a slot-die for coating adhesives to web-form material has particular
advantages over a multi roll applicator unit (calenderer). Web-form adhesive coating
speeds, when employing multi roll applicator units (calendars), are typically limited to 300
meters per minute. However, the use of slot-die coating technology, particularly when
318914
-7
Case 3:10-cv-00076-RLY-WGH Document 1-6 Filed 05/13/10 Page 12 of 12
FIG. 1
EXHIBIT G
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Case 3:10-cv-00076-RLY-WGH Document 1-7 Filed 05/13/10 Page 3 of 17
US 7,476,416 82
Page 2
OTHER PUBLlCAT10NS
6.251.517 HI 61200 I Sashihara d al.
6j06,447 1>1 1/2001 Hirsch er al. Angier, OJ, et al., "Mastication ofRubber. VI. Viscosity and Molecu
6,527.8')9 ill 3 /2003 Dietz ct al. lar Weight Relationships for Natural Rubber after Cold Mastication,"
6,759,122 Il2 7 /2004 Spies et al. Journal ofPolymer Science, vol, XXV, pp. 129-138 (l9'i7).
6,780,271 B1 8 /2004 Burmeister et al. Rauwendaal. C .. "The Multisercw Extruder with More Than Two
6,799,881 B2 10' 2004 r ischer Screws." Polymer Extrusion, Hanser Publishers, pp. 11-12 t 1986)
6,822,048 B1 1 Jl2004 Burmeister el al. Author Anonymous, "Adhesive compounding process for production
6,881,796 B2 4/2005 Yamaguchi et al. of prcssur42 sensitive tapes." published [It www.researchdisclosure.
2001'0039302 Al 11/2001 Wustling ct al. com (Oct. 3 L 2003).
Case 3:10-cv-00076-RLY-WGH Document 1-7 Filed 05/13/10 Page 4 of 17
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Case 3:10-cv-00076-RLY-WGH Document 1-7 Filed 05/13/10 Page 9 of 17
US 7,476,416 B2
1 2
PROCESS FOR PREPARING ADHESIVE
the process. TIle number of spindles influences the free vol
USING PLANETARY EXTRUDER
ume within the planetary mil extruder, the residence time of
the material in the process, and also determines the surface
REFERENCE TO RELATED APPLlCATION area for heat and material exchange. By way ofthe dispersive
" energy introduced, the number of planetary spindles has an
This application claims the benefit of U.S. Provisional influence on the result of compounding. Given a constant
Application No. 60/524.505, filed Nov. 24, 2003. diameter of roll cylinder, a larger number of spindles permit
better homogenization and dispersion or, respectively, a
1'1i.'LD 01; riu: INVIiNTlON
greater product throughput.
iu
111C present invention relates to a continuous, low-tem The maximum number of planetary spindles iustallable
perature process for the mastication and compounding of between the main spindle and the roll cyl indcr depends on the
non-thermoplasuc elastomers with tackitying resins and may diameter of the roll cylinder and on the diameter of the plan
include one or more of the following: thermoplastic elas crary spindles used. When using relatively large roll diarn
tomers. extenders, plasticizers and oils, activators, anti-de \ 5 ctcrs, as required fur obtaining production-scale throughputs,
gradents, crosslinking agents, colorants, solvents, and foam and/or relatively small diameters for the planetary spindles,
ing agents. In oue aspcct of the invention, the adhesive may be the roll cylinders can be equipped with a relatively large
applied directly to a web-form material. number of planetary spindles. With a roll diameter PI' D=70
The general purpose of the invention is to provide a method nun, typically up to seven planetary spindles arc used,
for producing a self adhesive composition by mastication of en whereas with a roll diameter of D=200 rum ten, tor example,
non-thermoplastic elastomers in a planetary roller extruder and a roll diameter of D~400 mrn 24 for example, plunctury
(PRE). In one embodiment mastication is achieved through spindles can be used. However. these examples arc in no way
the use of double transversal or "back-cut" planetary limiting to those skilled in the art. I'or example, ifthe diameter
spindles, in combination with full-flight planetary spindles 10 of the main spindle is smaller relative to a lnrgcr main spindle,
produce an adhesive that can he applied to a web-form mate
2:' the 11111nber ofplanetary spindles can be increased.
rial using a slot die.
Pressure sensitive adhesive compositions are blends of sev 3(1 The present invention is directed to a process lor preparing
era! raw materials including elastomers, resins, plasticizers an adhesive using a modified planetary roller extruder. The
and other additives such as antioxidants, fillers, pigments, etc. process in accordance with one aspect of the invention
Since these ingredients must be blended in the proper ratio to includes introducing primary raw materials including a nou
obtain the adhesive having the desired properties, the raw thermoplastic elastomer into a feeding section of the modified
materials arc typically blended with a mechanical mixer 35 planetary roller extruder, conveying the raw materials from
II nder controlled conditions as part of a balch-wise process to the reeding section to a compounding sectiou olthc modified
obtain a thoroughly mixed product having the appropriate planetary roller extruder.mixing the primary raw materials in
relative amounts of the raw materials. the compounding section, producing a homogeneous adhe
Planetary roll extruders have been known and have typi sive composition and applying the adhesive composition to a
cally been used in processing of thermoplastics such as PVC, 411 web- form material. The compounding section of the modified
for example, where they were used primarily to supply the
planetary roller extruder includes a main spindle surrounded
downstream units such as, for example, calendars or roll
by and intermeshed with a plurality of planetary spindles at
mills. Planetary roll extruders have typically been used to
least one of which is a double transversal mixing spindle
process heat-sensitive compounds with a minimum of dcgra
dation because thin layers of compound can be exposed to 45 having a plurality of back-cut helical flights.
large surface areas thereby resulting in effective heat In accordance with another aspect of the invention. the
exchange, mixing and temperature control, Planetary roll modified planetary roller extruder is used to produce an adhe
extruders are available in various designs and sizes. The sive composition. TIle process in accordance with this aspect
diameters of the roll cylinders, depending on the desired of the invention includes continuously metering into a plan
throughput, arc typically between 70 nun and 500 HUU. 5« etary roller extruder primary raw materia Is of an adhesive
Planetary roll extruders generally have a filling section and composition comprising a non-thermoplastic elastomer and a
a compounding section. The filling section typically includes tackifyiug resin, continuously mixing the raw male rials in a
a conveying screw to which certain raw materials are fed compounding section of the planetary roller extruder to Ionu
continuously. The conveying screw then passes the material a homogeneous adhesive composition wherein the com
to the compounding section. The compounding section " pounding section includes a main spindle surrounded by and
includes a driven main spindle and a number of planetary intcrmcshcd with a plurality o l'planctary spindles wherein at
spindles which rotate around the main spindle within a roll least one of the planetary spindles is a double transversal
cylinder with internal helical gearing. The rotary speed ofthe mixing spindle having a plurality of back-cut helical flights,
main spindle and hence the rotarioual speed of the planetary and continuously discharging the homogeneous adhesive
spindles can be varied and is one parameter to be controlled 6<1 composition from the extruder. In accordance with certain
during the compounding process. The materials me circulated embodiments, the self-adhesive composition may be applied
between the wain and planetary spindles, or belween the 10 a web-formed material using an applicator unit such as a
planetary spindles and the helical gearing of the roll section, slot-die applicator unit and subsequently crosslinked.
so that under the materials are dispersed to form a homoge In accordance with another aspect of the invention. the
neous composition. Ii' elastomer is masticated such that M" is reduced to less than
The number of planetary spindles rotating in each roll 1.000,000 as measured by (We. In other aspects of the inven
cylinder can be varied and thus adapted to the requirements of tion, the elastomer may be masticated to cause 11 reduction in
Case 3:10-cv-00076-RLY-WGH Document 1-7 Filed 05/13/10 Page 10 of 17
US 7,476,416 82
3 4
M; of more than about 50%, more particularly more than known as back-cut spindles or Noppenspindel) 28, or zoned
about 80%, relative to tile original M", tor the elastomer. helical flights (Igclspindcl), etc. TIle number of planetary
spindles chosen and their geometries (e.g., open vs. full
BRIEF DESCRIPTION OF THE DRAWINGS flight) can be manipulated in such a way as to influence the
dynamic discharging effect of each roller barrel section 20
An exemplary embodiment of the invention is explained in and the discharging differential between sections. Addition
more detail below with reference to the drawings in which: any. the gap between the dosing ring 22 and the main spindle
FI(;. I is a longitudinal sectional view ofa planetary roller 26 can be changed to vary the dynamic discharging effect or
extruder in accordance with one aspect of the present inven each barrel section 20 and the discharging differential
tion: III between the barrel sections 20.
FIG. 2 is an enlarged view of an exemplary double trans A standard planetary spindle 30 is represented by a cylin
versal mixing spindle; der in which g.woves or flights have been cut at 45° angles to
FIG. 3 is a cross-sectional view of a dosing ring from the the spindle ax is, the same angle as the main spindle flights.
planetary roller extruder in FIG. I; The planetary spindles ride in the main spindle flights and this
PIG. 4 is cross-sectional view of a slot die coater; I" design yields identical surface speeds or the planetary
FlO. 5 is a longitudinal sectional view ofa planetary roller spindles 28, 30 and the main spindle 26. There is a gap
extruder and slot die coater in accordance with one aspect of between the main and planetary spindles which is tilled with
the present invention: and process material and the net result is that ncar zero-shear
FlO. 6 is a cross-sectional view of the planetary roller distributive and dispersive mixing can occur between the
extruder in FIG. 1 along line 6-6. ell main spindle 26. the planetary spindles 28. 30, and the barrel
wall 24.
DETAILED DESCRIPTION OF THE INVPNTION Another net result ol the 45° angle cut into the planetary
and main spindles is a positive pressure. a forwarding motion
.\11 documents cited are, in relevant part. incorporated imparted on the process material. A variation which yields
herein by reference: the citation of any document is not to be e5 less pressure, more slippage, less forwarding motion. longer
construed as an admission that it is prior art with respect to the residence time and hence greater mixing is the usc of or
present invention. double transversal spindles 28 (also known as noppen
Turning now to the drawings, and referring initially to FIG. spindles or back-cut spindles).
1, n planetary roller extruder in accordance with one embodi I>oublc transversal planetary spindles 28 arc spindles hav
ment of the present invention is illustrated and generally 311 ing openings in the flights that penni! material to pass
designated by the reference 10. It will be appreciated that the between the wall of the barrel 24 and the main spindle 26 and
planetary roller extruder system 10 is illustrated in diagram slow the rate with which material pnsses through the plan
matic form in order to explain its operation in easily under etary roller extruder system 10. One example of a double
staudablc manner. However, in actual practice. tile shape and transvcrsnlspindle 28 is a so-called porcupine spindle. A par
size of the system 10 might be substantially different from .1" ticulnr cxumplc ola double transversal spindle 2N is shown in
that illustrated and yet still be within the scope of the claims detail in lK]. 2. back cut openings 32 increase residence time
set forth herein. and improve mixing. The design of a double transversal
TIle planetary roller extruder system 10 includes a feeding spindle 28 is a variation of the standard planetary spindle,
section 12 and a compounding section 14. 111eprimary adhc with the addition of channels cut into the 45" angled flights.
sive raw materials are added into the feed throat 16 and 411 The angle of these back cut channels can range from about
metered onto the conveying screw 18 ofthe tilling section 12. 45-135° relative to the spindle nights. more particularly from
As used herein. the term "primary raw materials" refers to about 75-105°, and in accordance with certain aspects of the
those materials of the adhesive formulntion added into the invention the back cut channels may be at an angle of about
feed section 12 of the planetary roller extruder 10. Primary 90°, The number and depth of these channels may also be
raw materials may include, but are not limited to. elastomers. 4" varied and can be de1ined in more simplistic terms by the
resins, extenders, activators. anti-dcgradcnts. and crosslink following: l(total channel area cut into the spindle flights/total
ing agents. 111e screw 18 conveys the primary raw materials area of spindle flights)x 100%]. This value may range Irom
into the compounding section 14. The compounding section about 10-90%. more particularly from about 40-60%, and in
14. as illustrated in FIG. 1, includes four planetary roller certain embodiments ofthe invention the value may be about
barrel sections 20a. 20h. 20, and 20d separated by dosing 511 50%. Planetary roller extruders having double transversal
rings 22a, 22b and 22,. Each roller barrel section 20 includes spindles 28 arc commercially available from Rust-Mitschke
a 45" helical toothed cylinder 24. a 45° helical toothed main Entex. By adjusting the number of fnll llight 30 and open or
spindle 26 and a plurality of 45° helical toothed planetary double trausversalspiudlcs 28. the rate with which material
spindles 2N. 30. The helical gearing can have any suitable passes through the planetary roller extruder and hence the
angle. for example. an angle of 10 to 60°, more particularly " amount of mastication that is done on the material can be
somewhat greater than 20° may be useful. In accordance with controlled.
the certain aspects of the present invention. at least one or the Conventional plnnetury roller extruders contain M least 3
roller barrel sections 20 includes a double transversal plan and can contain up to 24 spindles depending on the din meter
etary spindle 28. The present invention is not limited to the of the cylinder and process design. Of course. one of skin in
usc of donble transversal planetary spindles. Other spindle 611 the art would realize that a greater number of planetary
configurations that provide the desired levels of mixing can spindles could be nsed depending on the specific dimensions
also be used. and construction of the extruder, In one embodiment of the
The maximum number of planetary spindles 2N. 30 is a invention, a planetary roller extruder 10 having a 70 nun
function of the diameter of'thc main spindle 26 and the helical diameter cylinder having 6 spindles 2N. 30 is used. In accor
toothed cylinder 24. The planetary spindles 28, 30 can exhibit 0" dance with certain aspects ofthe invention. the double trans
many different tooth geometries. e.g .. ful I helical flights versal spindles 28 account for more than 20%. more particu
(Planetspiudel) 30. double transversal helical flights (also larly more than 50%. of the number of planetary spindles 2N.
Case 3:10-cv-00076-RLY-WGH Document 1-7 Filed 05/13/10 Page 11 of 17
US 7,476,416 B2
5 6
30 in the planetary roller extruder 10. FIG. 6 shows a cross and temperature-stable. UV rays as well can be used for
section for a planetary extruder in accordance with a particu crosslinking, in which case appropriate UV promoters, for
lar embodiment of the invention that includes four (4) double example such as Ebecryl140 from OC8, must be added to the
transversal planetary spindles 28 and two (2) full flight selt-adhesive composition. Chemical and/or thermally
spindles 30. induced crosslinking may also be used.
The rotation of the main spindle 26 causes the planetary The non-thermoplastic elastomer may be chosen from the
spindles 28, 30 to be set in rotational movement, as a resnlt of group of the natural rubbers or of the synthetic rubbers or of
the helical gearing of the main spindle 26 interacting with the any desired blend of'natural rubbers and/or synthetic rubbers,
helical gearing of the planetary spindles 28, 30. it being possible to choose the natural rubber or rubbers in
The planetary spindles 28, 30 also mesh with the internal 111 principle from all available grades, such as, for example,
gearing ofthe cylinder section 24. "111e helical gearing of the crepe, RSS. ADS, TSR, SIR 10. SIR 5L or CV grades.
main spindle 26. the planetary spindles 28, 30 and the cylin depending on the required purity and viscosity level, and it
der section 24 conveys the raw materials to be compounded in being possible to choose the synthetic rubber or rubbers from
the direction of the d ischarge orifice 34. the group of the randomly copolymerized styrene-butadiene
11lC term "secondary raw materials" as used herein refers 15 rubbers (SBR), butadiene rubbers (BR). synthetic polyiso
to raw materials or solvents introduced into the compounding prenes (lR). butyl rubbers (IJR), polyisobutylene rubber,
section 14 or the plunetary roller extruder 10. Secondary halogenated butyl rubbers (Xl lk). acrylate rubbers (ACM).
liquid materials. such 'IS liquid elastomers, molten resins, ethylene vinyl acetate copolymers (EVA) and polyurethanes,
oils. solvents, etc., can be introduced into the compounding and/or blends thereof.
section 14 via injection nozzles (not shown) through the :11 Thermoplastic elastomers with a weight fraction of Irom 1
dosing ring 22 assemblies. As shown in FIG. 3. the dosing to 100% by weight, based on the total non-thermoplastic
rings 22 include radially extending bores 23 that allow lor elastomer content. can be added to the non-thermoplastic
metered addition ofliquids to the compounding section 14.1u elastomers. As representatives, mention may be made <It this
accordance with one embodiment of the invention. the pro point in particular ofthe highly compatible styrene-isoprene
cess involves the feeding of solvent into the compounding :5 styrene (SIS), styrene-butadiene-styrene (SBS), styrene iso
section 14 of the planetary roller extruder 10 via the dosing prene butadiene styrene (SmS) grades as well as SFflS, and
rings 22. SEPS, and any combination thereof.
Secondary solid raw materials can be added to the com Tackifier resins which can be used arc, without exception,
pounding section 14 through a side feeder 36 or twin screw all tackifier resins that can function as tackifiers in the formu
dosing units 38. '111e twin screw dosing units 38 are typically 311 lation. 'lackifier resins may be present in the adhesive corn
positioned perpendicular to the axis of the compounding sec position at from 40% to 200% weight fraction based on elas
tion 14 and arc typically located near the beginning of the tomer. Representatives that may be mentioned include the
com pounding section directly adjacent to the dosing ring 220. rosins, their disproportionated. hydrogenated, polymerized
The twin screw dosing units 38 cau be employed to introduce and esterified derivatives and salts. the aliphatic and aromatic
solid components such as thermoplastic elastomers. resins, 35 hydrocarbon resins, terpene resins und terpene-phenolic res
extenders, activators. anti-degradents. crosslinkers, etc .. to ins. Typical resins include partially or fully hydrogenated
the individual roller barrel sections 20. wood, gum, or tall oil rosins. esterified wood, gum or tall oil
Another embodiment of the invention involves coating the rosins, alpha and beta pinene resins, and polyterpene resins.
self-adhesive composition on a web- form material, where the More specifically, resins useful herein include C5 hydrocar
coating of the web-form material may be carried out using 40 bon resins, C9 hydrocarbon resins and mixtures thereof Con
any of a variety of coating, techniques including" but not ruarouc indcuc and alpha-methyl styrene resins call also be
limit cd to, slot-die coating. roll-over-roll coating, reverse roll used. The resins can be introduced in both solid and molten
and knife-over-roll coating. In accordance with certain form. Any desired combinations of these and other resins can
embodiments of the present invention, the adhesive compo be used ill order to adjust the properties of the resultant
sition is applied to the web-form material using a slot-die 45 adhesive composition in accordance with what is desired.
applicator unit. Particularly useful methods for applying the Reference may be made expressly to the depiction of the state
adhesive composition to the web-form material include slot of knowledge in "Handbook of Pressure Sensitive Adhesive
die coating using a rotating lip die or a fixed lip contact die. Technology" by Donatus Satas (van Nostrand, 1989).
One particular slot die unit that can be used is a rotating lip die Typical extenders include clays, calcium carbonate, talc,
having a spindle that trails the die lip. One example of such a 50 and aluminum hydrates. Typical activators include zinc
die is commercially available from SIMPLAS and is shown in oxide, zinc chloride, magnesium chloride and magnesium
FI(r. 4. Rotating lip die 40 includes an inlet 42 for receiving oxide. Typical anti-degradcnts include antioxidants (AO),
the adhesive composition from the extruder 10. As shown in ultraviolet absorbers (UVA), and ultraviolet stabilizers
FIG. 5, the adhesive composition is continuously conveyed (lNS). Typical opacifiers and colorants include. but are not
from the extruder 10 to the rotating lip die applicator 40 to be " limited to, titanium dioxide and other various metal pigments
applied to a web-form material through slot 44. '111e rotating known to those skilled in the art.
lip die applicator 40 further includes a rotating spindle 46 at Typical solvents are non-polar aromatics and aliphatic>
the trailing edge ofthe die lip that improves coating properties such as acetone, toluene, hexane, heptane, and blends thereof.
of the applied adhesive. Adjustable bolts 48 on the rotating lip When a highly foamed adhesive is desired. the solvent con
die applicator 40 enable the operator to easily adjust the lip 60 tent of the adhesive may be increased. This aspect of the
opening and control the adhesive coating thickness. disclosure overcomes the problems typically encountered
In accordance with another aspect of the present invention, with typical hot melt adhesives that experience problems
the self-adhesive composition may be crosslinked. More spe caused by the higher densities and smooth. non-extensible
cifically the coated adhesive composition may be crosslinked surfaces of extruded adhesives which result in a low ratio of
with the aid of electron beams or IN rays by means of I>.i tack to adhesion in the finished adhesive. Solvents, when
ionizing radiation. such as electron beams. for example, so present ill the formulation, may be used in any amounts lip to
that the resultant self-adhesive tape becomes shear-resistant about 70"10, more particularly up to about 50%, by weight of
Case 3:10-cv-00076-RLY-WGH Document 1-7 Filed 05/13/10 Page 12 of 17
US 7,476,416 B2
7 8
the adhesive composition. Typical liquid elastomers are low extruder, Second, solid resin, as opposed to molten resin can
molecular weight natural rubber and low molecular weight be introduced into the compounding section. The solid resin
synthetic polyiosoprene and polybutene rubbers. Typical oils bas a viscosity that more closely resembles the elastomer,
can be paraffinic, isoparalfinic, naptheuic, aromatic, or pol when compared to molten resin. As a consequence. the addi
yaromatic. Examples of foaming agents include Cellogen tion of solid (as contrasted with liquid) resin further enhances
foaming agents and gases. mixing efficiency. whereas molten resin tends to act as a
Plasticizers which can be used are all plasticizing sub lubricant and retards mixing efficiency. Additionally, the
stances known from adhesive tape technology. Examples of solid resin has a specific heat which affords it the ability to act
useful plasticizers include. but arc not limited to, the paraf as a heat sink. i.c, take heat away from the process, thereby
finic and naphtheuic oils. (functionalized) oligomers such as III minimizing the temperature of the melt during the com
oligobutadiencs and oligoisoprenes, liquid nitrile rubbers, pounding process. Conversely, molten resin increases the
liquid terpene resins, animal and vegetable oils and fats, temperature of the melt in the compounding process.
phthalates. and functionalized acrylates. The introduction of solvent into the compounding sections
Simply stated. some advantages ofcertain embodiments of has several advantages. First. small amounts (e.g .. typically
the new invention/method include: I) purposeful. effective, I"10 to 20% by weight but amounts up to 50% could lcasibly be
and efficient mastication of non-thermoplastic elastomers, 2) nscd) of solvent. introduced to the adhesive through several
the introduction of various solid raw materials into the com dosing rings, enhances mixing efficiency, i.e. maintains
pounding section, 3) the introduction of solvent into the com homogeneity, while significantly lowering the viscosity ofthc
pounding section, and 4) the use of slot-die coating technol finished adhesive. 111e solvent is readily absorbed by the
ogy to achieve an adhesive coated web-form material with a 211 adhesive composition and the incorporation o I'solvent lowers
unique balance of converged panel adhesion and quick stick the resultant homogeneous adhesive's viscosity to the point
properties. that its application to a wcb-Iorm matcrial is not restricted to
The purposeful mastication of non-thermoplastic elas a multi-roll applicator unit (calendar). Rather. the lower-vis
tomers is accomplished as the elastomers arc forced with the cosity adhesive can now be applied to web-form material via
single-screw from the feeding section between the dosing 25 slot-die. reverse roll, roll-over-roll, knife-over-roll, or any
ring and the main spindles into the compounding section, number oftraditional adhesive application techniques includ
where it is intensively mixed and subsequently masticated. ing the use of multi-roll applicators. The subsequent libera
Tile degree of mastication is further enhanced through the use tion of the soJvent from the adhesive that has been applied to
of double transversa! planetary spindles. Another Iactor that the web-form material affords the ability to affect numerous
affects the amount of mastication is the internal diameter of 31l adhesive surface geometry profiles, i.e. degrees of foaming,
the stop ring. By narrowing the gap between the stop ring or in the adhesive film. Subsequently. the performance proper
dosing ring and the spindle, more mastication can be per ties of tile adhesive film can be further manipulated, i.e. in
formed. Mastication of the non-thermoplastic elastomer addition to degree of elastomer mastication and formulation.
translates into more efficient compounding of the elastomer The use of a slot-die for coating adhesives to web-form
with other solid and liquid materials. yields the potential for a 3" mutcrial bas particular advantages over a mull i mll applicator
greater ratio of tack to adhesion in the finished adhesive and unit (calendar). Web-form adhesive coating speeds. when
yields a finished adhesive with lower viscosity that is not employing multi roll applicator units (calendars). are typi
limited to being coated via a multiple roll applicator unit cally limited to 300 meters per minute. However. the use of
(calendar). This provides an opportunity to employ more slot-die coating technology, particularly when employed in
prevalent. or existing coating equipment. as opposed to pur 40 conjunction with lower-viscosity. high-solids adhesives, e.g.
chasing a rnuhiple-ro ll coating unit. 80-90%. as opposed to higher-viscosity. 100% solids adhe
ln accordance with one aspect nf the invention, the clas sives. is of particular interest, as application speeds easily
tomer is masticated such that M", is reduced to less than approach 500 meters per minute or more.
I ,000.000 as measured by GPc. In other aspects ofthe inven The process of the invention permits the production of
tion. the elastomer may be masticated to cause a reduction in 45 high-performance self-adhesive compositions and, espe
M". of more than a bout 50%, more particularly more than cially in conjunction with a downstream coating and
about gO%, relative to the initial M". for the elastomer. The crosslinking unit, permits the production of high-perter
initial molecular weight refers to the molecular weight of the mance scl l-udhcsivc tapes accompanied by particular cost
non-thermoplastic elastomer as it is being introduced into the advantages.
planetary roller extruder. As such. the initial molecular 51) In the first process step, a composition comprising the
weight may already have been reduced [IS a result of prepro elastomers and the known adjuvants required Ior the produc
cessing of the elastomer as compared to the molecular weight tion of self-adhesive compositions. such as extenders, anti
for the unprocessed elastomer. Therefore, the reduction in oxidants, activators. colorants, ageing inhibitors. plasticizers
molecular weight referred to herein is based 011 the reduction and tackifier resins, is produced in a planetary roll extruder,
in molecular weight obtained by processing on the planetary 55 the composition having a final temperature of less than 150 0
roller extruder. The reduction in molecular weight as C., typically less than 130° C. and, more particularly. between
described herein is calculated by l-ormuln I: about 25° C. and 100° C. The overall residence time ofthe
composition in the planetary roll extruder wiJl typically not
IJI
exceed about three minutes.
111e introduction of various solid raw materials into the 60 In accordance with certain aspects of the invention, the
compounding sections has several advantages. First, all solid adhesive formulation from the extruder is applied to a web
materials do not have to be introduced all at once in the Iorm material. This can be done in a particularly effective and
feeding section of the planetary roller extruder. i.e .. they can advantageous manner using a slot-die applicator unit. espe
be dosed ill one or more of the roller barrel sections of the cially using a rotating lip slot-die applicator unit similar to
compounding section. This gives the elastomer more time to 1i5 that shown in fIcr. 4.
be masticated prior to the addition of solid raw materials and In accordance with another aspect of the present invention,
increases the mixing efficiency of the planetary roller the self-adhesive composition may be crosslinked using eJec
Case 3:10-cv-00076-RLY-WGH Document 1-7 Filed 05/13/10 Page 13 of 17
US 7,476,416 B2
9 10
tron beams or UV rays to provide a self-adhesive tape having skill of those in the art, can be undertaken without departing
the desired properties. For further improved performance, Of from the spirit and scope of this invention.
in the ease of Electron Beam (EBC)-sensitive carriers,
crosslinking can also be carried out by means of'heat-activat EXAMPLES
required for this purpose can be done with the aid of the
known techniques. especially with the aid of high-tempera
ture duels, or else with the aid of infrared lumps. or by means IU
of high-frequency magnetic alternating fields, examples Ground Ground
being l lf waves. UIIP waves or microwaves. Natural Rubber
Rnbhcr Adhesive
Crosslinking of the pressure-sensitive adhesive composi
tion can be carried out. furthermore. by means of a combina Rubber (Kg/hr) 17.1
tion of ionizing radiation and hcat-activatablc chemical J 5 Resin (Kg/hr) 22.2
TiO} + antioxidant (Kg/hr) 1).7
crosslinkers. The result may be a highly shear-resistant pres Scr~w Speed (rpm) 71)
sure-sensitive self-adhesive composition. FoB curing sets the Adhcsive temp. between h:IITeI 72 l'.
adhesive so that it can be converted while having a residual cylinder 1&2
Adhesive temp, between barrel N/A 52' C.
latent hcat-activatable curing agent available for end use L:ylindcI2&3
application. 2CJ Adhesive outlet temperature 86' C.
Extruder Residence Time (5) 1)0
For the purpose of heat-induced and/or chemical crosslink
Adhesive homogeneity lvo gets
ing. it is possible in the process of the invention 10 use all Mw(GPL'j 4,136,1 lU ~U2. 74~
known heat-nctivatnble and/or chemical crosslinkers, such as Percent Drop in Mw ~1).6°·o
other films, foam materials in web form, made from polyeth Adhesive
us 7,476,416 B2
11 12
ground to an average particle sizeof8 nun with talc used as an
anti-agglomerating agent. The C5 resin was added in flake -continued
form and antioxidant was introduced as a powder. The adhe
sive row materials were all added into the feed throat of a 70 Pelletized
Rubber
into an adhesive after being mixed in the first of three 400 nun
barrel sections each containing 2nonnal and 4 double trans Screw Speed (rpm) 144
Adhesive temp. between barrel cylinder 1&2 64" C,
versal mixing spindles rotating at 65 rpm. The entire cornplc Adhesive temp, between barrel cylinder 2&3 2')" C.
rncnt ofsolvent was added viu an injcction valve inserted into Adhesive outlet temperature :N~ c.
a dosing ring. The finished adhesive was determined to be 111 Extruder Residence Time (1') 120
completely solvated and homogeneous (gel free). Adhesive homogeneity No gels
Example 5
A standard masking tape adhesive was produced with the J5
PRE having three barrel cylinders. represented by 100 phr
natural rubber. lIS phr C5 resin, 50 phr kaolin clay, 5 phr
ZnO. 2.5 phr Ti02, and 2 phr antioxidant. The rubber used in
this adhesive was SIR 5L, pre-masticated and blended with 2 Ground
~IS au anti-agglomcrauug agent. The C5 resin was added in Rubber and Antioxidant (Kg/hr) t4.76
flake form. and the 7nO and Ti02 were intrndueed as pow Resin - Fccdthroar (Kg-hn R.!)!)
ders. The adhesive raw materials were all added into the Resin - SIJefeedcr (Kg-hr l ~.64
Iccdrhroat or a 70 nun PRE. The raw materials were subse- l-il'c r. 7110, Ti02 (Kg/hr) g.12
45
Solvent - Toluene ~ ':;"3 tKg/llfJ 11.1)
quently compounded into an adhesive after being mixed in Solvent - Tolucuc . 3i -l tKg/hr) 19.0
three 400 m III barrel sections each containing 2 normal and 4 Screw Speed (rpm) 141
double transversal mixing spindles rotating at 70 rpm. 111e Adhesive temp, between barrel cylinder 1&2 110 C
finished adhesive W[lS determined to be completely hornoge Adhesive temp, between barrel cylinder 2&3 61\ r.
Adhesive temp, between barrel cylinder 3&4 33" C.
ncous (gel free). Subsequent molecular weight analysis ofthe 51) Adhesive outlet temperature II r C.
adhesive was completed via gel penn eat ion chromatography Extruder Residence Time (5) 73
(GPC) and thermal field 110w analysis (ThFFF). The molecu Adhesive homogeneity No gels
lar weight analysis indicated that the natural rubber had been
reduced in mulecular weight by approximately 50%. A standard masking tape adhesive was produced with the
i5 PRF having fOUT barrel cylinders, represented by 100 phr
Example 4 natural III bber, 115 phr C5 resin. 50 phr kaolin clay. 5 phr
InO, 2.5 phr Ti02. and 2 phr antioxidant. The rubber used in
this adhesive was SIR 10, ground to an average particle size of
8nlln with talc used as au anti-agglomerating agent. A portion
60 of the C5 resin was added in flake fonn into the feedthroat of
yer.erized
Rubber
a 70 mm PRE, along with the ZnO and Ti02 powders. The
Adhesive raw materials were subsequently mixed in the first offour 400
mm barrel sections each containing 2 normal and 4 double
Rubber and Antioxidant (Kg/hr) 14.08
Resin (Kg/hr) 15.88
transversal mixing spindles rotating at 141 rpm. The remain
hiler, ZnO, TiO=' (Kg/lIn 7.93 6." ing flake resin was added via a side feeder located immedi
Solvent - Tol1l011e (KWhr) 4().(J ately upstream from the first dosing ring and subsequently
mixed ill the second barrel section. Solvent was added via
Case 3:10-cv-00076-RLY-WGH Document 1-7 Filed 05/13/10 Page 15 of 17
US 7,476,416 B2
13 14
injection valves inserted into dosing rings, with II kg/hr 14. The process of claim 1 wherein the elastomer is mas
added into the dosing. ring located between barrels 2&3 and ticatcd such that M w is reduced to less than 1,000,000 as
29 kg/hr being added into the dosing ring located between measured by (iPe.
barrels 3&4. The finished adhesive was determined to be 15. "TIle process or claim 1 wherein the non-thermoplastic
completely homogeneous and solvated (gel free). 5 elastomer is selected from the group consisting of natural
Having described various aspects and embodiments olthe rubber, synthetic polyisoprene, styrene butadiene rubber.
invention aud several ndvantages thereof, it will be recog butyl rubber, polyisobutylenc rubber. and combinations
nized by those of ordinary skills that the invention is suscep thereof.
tible to various modifications. substitutions and revisions 16. The process of claim 1 wherein the step of applying the
within the spirit and scope of the appended claims. 10 adhesive composition to a web-form material comprises a
coating process selected from the group consisting of slot-die
What is claimed is: coating, reverse roll. roll-over-roll coating and knife-over-roll
I. A process for preparing an adhesive, the process com coaling.
prising the steps of: 17. The process of claim 16 wherein the coating process
a.) introducing primary raw materials comprising a non 15 comprises slot-die coating using a rotating lip die or a fixed lip
thermoplastic elastomer into a feeding section of il plan contact die.
b.) conveying the primary raw materials from the feeding f.) crosslinking the adhesive composition.
section to a compounding section of the planetary roller 19. The process of claim 18 wherein step f comprises
extruder; 211 crosslinking the adhesive composition using a process
c.) mixing the primary raw materials in the compounding selected from the group consisting of EB crosslinking, VV'
section, wherein the compounding section comprises a crosslinking, thermal and/or chemical crosslinking and corn
main spindle surrounded by and intermcshed with a binarions thereof.
plurality o lplanetary spindles wherein at least oue of the 20. The process of claim 1 wherein the non-thermoplastic
planetary spindles is a double transversal mixing spindle :25 elastomer has all initial molecular weight (Mldmlriall) bclor
comprising il plurality of back-cut helical flights;
processing and a final molecular weight (Mw(lin"ll) after pro
d.] producing a homogeneous adhesive composition: and cessing and said non-thermoplastic elastomer cxibits a %
e.) applying the adhesive composition to a web-form mate reuctiou in M",ofmore than about 50% as caculated in accor
rial. dance with Formular I:
2.lhe process ofclaim l wherein the compounding section 311
(II.
comprises from 3 to 24 planetary spindles.
3. The process of claim l wherein the compounding section 21 . A process for producing an adhesive composition com
further comprises planetary spindles having Ii.IlI helical prising:
flights. a.) continuously metering into a planetary roller extruder
4. The process of claim 3 wherein the double transversal 35 primary raw materials of an adhesive composition com
mixing spindles account for more than 20 percent of the total prising a non-thennoplastic elastomer and a tackilying
number of planetary spindles in the compounding section. resin;
5. The process ofclaim4 wherein the compounding section b.) continuously mixing the primary raw materials in a
comprises twice as many double transversal spindles as compounding section of the planetary roller extruder to
4(1
spindles having full helical flights. form a homogeneous adhesive composition wherein the
6. The process of claim 1 further comprising adding sec compounding section comprises a main spindle sur
ondary raw materials to the compounding section. rounded by and intermeshed with a plurality ofplanetary
7. The process of claim 6 wherein the secondary raw mate spindles wherein at least one of the planetary spindles is
rials comprise solid raw materials selected from the group a double transversal mixing spindle comprising a plu
consisting of thermoplastic elastomers, tackifying resins, 45 rality of back-cut helical flights: and
extenders. activators. crosslinkers, colorants. and mixtures c.) continuously discharging the homogeneous adhesive
thereof. composition from the extruder.
8. 111eprocess of claim 6 wherein the secondary raw mate 22. The process of claim21 wherein the non-thermoplastic
rials comprise liquid raw materials selected from the group '0 elastomer is selected from the group consisting of natural
consisting of liquid elastomers, molten resins, oils, solvents rubber. synthetic polyisoprcnc, styrene butadiene rubber.
and mixtures thereof. butyl rubber, polyisobutylcne rubber, and combinations
9. The process of claim 8 wherein the solvent is selected thereof
lrom the group consisting or acetone, toluene, hexane, hep 23. The process of claim 22 wherein the uon-therinoplustic
tane. and mixtures thereof " elastomer comprises pre-masticated natural rubber.
10. The process of claim I wherein the compounding sec 24. The process of claim 2l wherein the compounding
tion comprises a plurality of roller barrel sections. sections comprises a plurality of roller barrel sections.
II. The process of claim 10 wherein each barrel section 25. The process of claim 24 wherein each roller barrel
comprises a double transversal spindle. section comprises at least one double transversal mixing
12. The process of claim 1 wherein the primary raw mate 611 spindle.
rials comprise natural rubber and tackifying resin. 26. TIle process of claim 21 further comprising adding
13. The process of claim 11 wherein the primary raw mate solvent to the raw materials in the compounding section.
rials further comprise an activator selected from the group 27. '111e process of claim 21 further comprising:
consisting of zinc oxide.magnesium oxide and combinations d.) applying the adhesive composition to a web-form mate
thereofand an extender selected from the group consisting of Ii' rial.
clays. calcium carbonate. talc, aluminum hydrates and C0111 28. '111e process of claim 27 wherein the adhesive compo
US 7,476,416 B2
15 16
process selected from the group consisting ofslot-die coating, 32. The process of claim 31 wherein the secondary raw
reverse roll, roll-aver-roll coating and knife-aver-roll coating, materials comprise solid materials.
29. The process of cia im 27 wherein the web- form material 33. The process ofclaim 32 wherein the solid materials are
selected tram the group consisting of thermoplastic elas
selected from the group consisting of paper, polyethylene,
tomers, resins, extenders. activators, anti-dcgradcnts,
polypropylene, polyester. polyvinylchloride and combina crosslinkers and mixtures thereof.
tions thereof 34.lhe process of claim 32 wherein the compounding
30. The process of claim 29 further comprising crosslini section further comprises a twin screw dosing unit and the
king the adhesive couipositiou. solid materials are added to the compounding section via the
31. The process of claim 21 further comprising adding 10 twin screw dosing unit.
secondary raw materials to the compounding section.
* * * * *
Case 3:10-cv-00076-RLY-WGH Document 1-7 Filed 05/13/10 Page 17 of 17
It is certified that error appears in the above-identified patent and that said Letters Patent is
hereby corrected as shown below:
Claims:
JOH:'I DOLL
Acting Director oft/If: United States Palen! and Trademark 0.llicl'