EP0624666A1 - Dispositif et procédé pour le frisage et la reticulation de fibres - Google Patents

Dispositif et procédé pour le frisage et la reticulation de fibres Download PDF

Info

Publication number
EP0624666A1
EP0624666A1 EP93850102A EP93850102A EP0624666A1 EP 0624666 A1 EP0624666 A1 EP 0624666A1 EP 93850102 A EP93850102 A EP 93850102A EP 93850102 A EP93850102 A EP 93850102A EP 0624666 A1 EP0624666 A1 EP 0624666A1
Authority
EP
European Patent Office
Prior art keywords
fiber
tow
crimper
fibers
stuffer box
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP93850102A
Other languages
German (de)
English (en)
Other versions
EP0624666B1 (fr
Inventor
Michael Rowland
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
R K Carbon Fibers Ltd
Original Assignee
R K Carbon Fibers Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by R K Carbon Fibers Ltd filed Critical R K Carbon Fibers Ltd
Priority to AT93850102T priority Critical patent/ATE162562T1/de
Priority to DE69316592T priority patent/DE69316592T2/de
Priority to EP93850102A priority patent/EP0624666B1/fr
Publication of EP0624666A1 publication Critical patent/EP0624666A1/fr
Application granted granted Critical
Publication of EP0624666B1 publication Critical patent/EP0624666B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/12—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics using stuffer boxes

Definitions

  • the present invention relates to an apparatus and process for providing crosslinked fibers with non-symmetrical crimps. More particularly, there is provided an apparatus and process for crimping crosslinked fibers of tows of fibers which act as if they were crosslinked wherein the crimps are set by further heat treatment.
  • Crimp can be defined as the non-linearity in fiber. For most of the man-made fibers employed in carpet manufacture, a non-woven battings, the crimp or bend in the fiber is induced by thermal/mechanical techniques. It can also be thought of as the difference between the non-linear (crimped) fiber and the straightened fiber (fiber extended). A crimp is important in carpet fibers and non-woven applications because it provides bulk to the yarn by preventing two fibers from laying parallel to one another. As a result, the carpet tuft will have greater covering power, appear softer, and give better resistance to wear and abrasion, among other benefits.
  • Crimp is also useful in the processing of staple fibers. Crimp is particularly useful in the processing of high modulus fibers which are difficult to work with because of slipperiness.
  • Thermoset fibers such as carbon fibers and related fibers although relatively uncommon do not crimp since they do not soften or melt. Heat, steam, and pressure do not create crimp in carbon fiber, carbonaceous fibers (>65% carbon) or any other thermoset fiber.
  • Crimp in the stuffer box is achieved by passing yarn(s) or tow(s) into a uniformly heated chamber which is at the tempeature required to heat set the fibers in their crimped or non-linear configuration. Steam is usually used to assist and lubricate. As the yarns are forced into the chamber by feed rolls, it pushes against yarn which is already in the chamber, thereby causing the filaments to bend and buckle (crimp).
  • a weight tube fitted into the top of the stuffer box governs the flow and quantity of yarn into the stuffer box.
  • the frequency (crimps per inch) and the crimp amplitude of the fibers are controlled by regulating the speed of the feed rolls to that of the take up rolls as well as the weight of the tube. Crimp setting by these techniques can be done for single filaments or on multiple ends (tow) using the spunize technique.
  • the crimps are generally characterized by numerous sharp bends.
  • U.S. Patent No. 4,868,038 of McCullough et al which is herein incorporated by reference, discloses one method for preparing novel non-linear carbonaceous fibers having physical characteristics resulting from heat treating stabilized polymeric fibers in the form of a knitted fabric. There is described a proccess wherein the fabric is substantially irreversible heat set under conditions free of non-uniform stress and tension. In order to obtain fibers which are non-linear, it is necessary to deknit the continuous fibers and then chopping to the desired length. Knitting and then dekinitting the fabric to obtain non-linear carbonaceous fibers increases the cost in producing the fibers. This crimp is permanent and will not disappear on subsequent heat treatments.
  • U.S. Pat. No. 2,245,874 to Robinson discloses a method for forming curled fiber material by passing fibers over rollers under conditions to bend and stretch the fibers beyond elastic limits. Such a process cannot be used to produce the non-linear fibers of the invention. This crimp can be removed by heating the fiber crimped up to the glass transition point.
  • U.S. Pat. No. 2,623,266 to Hemmi discloses the mechanical preparation of sinusoid or spiraloid crimped fibers.
  • the fibers are heated and passed through a series of bars which impart a meander-like crimp.
  • the fibers are formed in a crimped and stretched state. It is desirable to provide a relatively inexpensive and simple method for producing non-linear fibers and tows.
  • the present invention is directed to a process and an apparatus for forming non-symmetrical substantially permanent heat set crimps in crosslinkable fibers or tows which are capable of further crosslinking at eleveated temperatures.
  • the process of the invention comprises the steps of:
  • This process can be used with any fiber which will undergo some crosslinking by heat treatment.
  • the process of the invention is particularly useful for crimping partially crosslinked fibers, such as oxidized polyacrylonitrile fibers, or those fibers which act as though crosslinked, such as p-aramid fibers, which are liquid crystals or have a higher melt point.
  • the apparatus of the invention comprises:
  • EMI electromagnetic interference
  • Fig. 1 schematically illustrates the apparatus and process of the invention.
  • a tow 10 of precursor fibers is first past through a heater 12 to soften the fibers.
  • the heater 12 is provided with steam jets 13 which are used when the tow comprises oxidized polyacrylonitrile based fibers.
  • the heated fiber 10 is fed into a crimper stuffer box 16 with feed or draw-in rolls 14, 14A.
  • the feed rolls 14,14A are preferably heated such as with steam to maintain the fibers in a softened state when fed into the crimper stuffer box 16.
  • the crimper stuffer box 16 is provided with a pair of doctor blades 15,15A which function to feed the tow into the crimper stuffer box 16 and to apply pressure to the fibers.
  • the pressure is applied by having one of the blades 15, 15A being hinged and acting as a clapper bar.
  • the pressure can be applied with spring means, weights 17, as shown in the drawing, or any suitable means.
  • a pressure of about 10 to 50 kg has been found to provide a suitable crimp for oxidized polyacrylonitrile fibers. Crimp in the tow is formed in the crimper box 16 at the tangent point of the rolls 14,14A.
  • the collection of the tow 10 in the crimper box 16 causes a back pressure to develop whereby the tow 10 forms a crimp.
  • the width and depth of the crimper box 16 influences the type of crimp. Steam from jets 19,19A applied before and during crimping also has an effect on the amount of crimp set.
  • a conveyor 20 which catches the crimped tow 10' from the crimper box 16 and delivers it without tension or stress to a oven 18 having a plurality of heating zones 18a, 18b, 18c.
  • the first heating zone 18a is primarily to dewater the tow 10'.
  • the other zones 18b, 18c are used to heat treat the crimped tow 10' in an inert atmosphere so as to heat set and/or carbonize the tow 10'.
  • the tow 10' from the heater 18 is preferably cooled by a blower 21 before take-up on the take-up roll 22 which is synchronized with the conveyor speed to prevent tension or stress on the fiber.
  • the oxidized fibers are heated to temperatures of 300° to 1400°C in a non-oxidizing atmosphere such as nitrogen, argon or helium.
  • the carbonizing zone may be a single or multigradient furnace comprising a number of heating zones.
  • the inert gases can be supplied through the opening of the heating zone or may be injected at various points along the way of the fiber path.
  • Polymeric precursor material for the stabilized polyacrylonitrile fibers and tows which are advantageously utilized in preparing the carbonaceous fibers of the invention are selected from one or more of the following: acrylonitrile homopolymers, acrylonitrile copolymers and acrylonitrile terpolymers.
  • the copolymers preferably contain at least about 85 mole percent of acrylonitrile units and up to 15 mole percent of one or more monovinyl units of styrene, methyl acrylate, methyl methacrylate, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl pyridine and the like copolymerized therewith.
  • the acrylic filaments can also comprise terpolymers wherein the acrylonitrile units are at least about 85 mole percent.
  • the fibers can be formed by conventional methods such as in Patent No. 4,837,706 by melt, dry or wet spinning a suitable liquid of the precursor material.
  • the polyacrylonitrile (PAN) based fibers which have a normal nominal diameter of from 4 to 25 micrometers are collected as an assembly of a multiplicity of continuous filaments in tows.
  • the fibers are than stabilized, for example by oxidation or any other conventional method of stabilization.
  • the stabilization fibers or tows which are typically made from chopped or stretch broken fiber staple are processed according to the invention and heat treated at elevated temperatures in an inert non-oxidizing atmosphere for a period of time to produce a heat induced thermoset reaction. Typically, nitrogen content for the fiber of between about 5 to 35% is maintained.
  • the fibers are generally provided with a substantially permanent or irreversible heat set.
  • the resulting tows or fibers may be used per se.
  • the carbonaceous fibers derived from oxidized polyacrylonitrile based materials which provided by the invention are classified into three groups.
  • the carbonaceous fibers have a carbon content of greater than 65% but less than 85%, are electrically nonconductive, and do not possess any electrostatic dissipating characteristics, i.e., they are not able to dissipate an electrostatic charge.
  • electrically nonconductive as utilized in the present invention relates to a resistance of greater than 4 x 106ohms/cm(107ohms/in) when measured on a 6K (6000 filaments) tow of individual fibers having a diameter of from 4 to 20 microns.
  • the carbonaceous fibers are classified as being partially electrically conductive (i.e., having a low conductivity) and having a carbon content of greater than 65% but less than 85%.
  • the percent nitrogen content of such fibers is generally 16 to 20%.
  • Low conductivity means that a 6K tow of fibers in which the individual precursor fibers have a diameter of from 4 to 20 micrometer, has a resistance of from 4X106 to 4X103 ohms/cm (107-104 ohms/in).
  • the fibers having a carbon content of at least 85 percent but less than 92% and a nitrogen content of at least 5%. These fibers are characterized as having a high electroconductivity. That is, the fibers have an electrical resistance when measured on a 6K tow of less than 4X103 ohms/cm (104 ohms/in).
  • the non-symmetrical electrically conductive carbonaceous fibers are useful in EMI shielding.
  • Para-aramids which are processed according to the invention need only be carbonaceous in an amount of about 0.5 to 5%, preferably, about 1 to 3% to obtain a substantially permanent crimp.
  • Polyparabenzamide and their processes of preparation are disclosed in U.S. Pat. Nos. 3,109,836, 3,225,011; 3,541,056; 3,542,719; 3,547,895; 3,558,571; 3,575,933; 3,600,350; 3,671,542; 3,699,085; 3,753,957; and 4,025,494.
  • Polyparaphenylene terephthalamide (p-aramid) is available commercially as KEVLAR, a trademark of E.I. duPont de Nemours, and processes of preparing the same are disclosed in U.S. Pat. Nos.
  • wholly aromatic polyamides are poly(2,7-phenanthridone)terephthalamide, poly(paraphenylene-2, 6-naphthalamide), poly(methyl-1,4-phenylene) terephthalamide. Additional specific examples of wholly aromatic polyamides are disclosed by P.W. Morgan in "Macromolecules," Vol. 10, No. 6, pp. 1381-90 (1977).
  • the p-aramids fibers of the invention should be heat treated at a temperature above 200°C., preferably at a temperature of from 200°C, to 500°C., and more preferably from 200°C to 375°C.
  • the Period of heating depends upon, the temperature, size of fiber, type of aromatic polyamide etc.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Inorganic Fibers (AREA)
EP93850102A 1993-05-10 1993-05-10 Dispositif et procédé pour le frisage et la reticulation de fibres Expired - Lifetime EP0624666B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AT93850102T ATE162562T1 (de) 1993-05-10 1993-05-10 Vorrichtung und verfahren zum kräuseln und zur vernetzung von fasern
DE69316592T DE69316592T2 (de) 1993-05-10 1993-05-10 Vorrichtung und Verfahren zum Kräuseln und zur Vernetzung von Fasern
EP93850102A EP0624666B1 (fr) 1993-05-10 1993-05-10 Dispositif et procédé pour le frisage et la reticulation de fibres

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP93850102A EP0624666B1 (fr) 1993-05-10 1993-05-10 Dispositif et procédé pour le frisage et la reticulation de fibres

Publications (2)

Publication Number Publication Date
EP0624666A1 true EP0624666A1 (fr) 1994-11-17
EP0624666B1 EP0624666B1 (fr) 1998-01-21

Family

ID=8215307

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93850102A Expired - Lifetime EP0624666B1 (fr) 1993-05-10 1993-05-10 Dispositif et procédé pour le frisage et la reticulation de fibres

Country Status (3)

Country Link
EP (1) EP0624666B1 (fr)
AT (1) ATE162562T1 (fr)
DE (1) DE69316592T2 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3965547A (en) * 1970-04-06 1976-06-29 John Heathcoat & Co. Ltd. Apparatus for producing bulked yarns
US4004330A (en) * 1972-01-03 1977-01-25 Techniservice Division Textured Yarn Co., Inc. Textile treatment apparatus
EP0119521A2 (fr) * 1983-03-11 1984-09-26 Bayer Ag Procédé en continu pour la fabrication de fibres et fils en polyacrylonitrile
WO1990001578A1 (fr) * 1988-08-10 1990-02-22 Philip Morris Products Inc. Fibres textile crepees et appareil presse-etoupe et procedes servant au crepage de fibres textile
US4979274A (en) * 1989-04-18 1990-12-25 The Dow Chemical Company Process and apparatus for crimping fibers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3965547A (en) * 1970-04-06 1976-06-29 John Heathcoat & Co. Ltd. Apparatus for producing bulked yarns
US4004330A (en) * 1972-01-03 1977-01-25 Techniservice Division Textured Yarn Co., Inc. Textile treatment apparatus
EP0119521A2 (fr) * 1983-03-11 1984-09-26 Bayer Ag Procédé en continu pour la fabrication de fibres et fils en polyacrylonitrile
WO1990001578A1 (fr) * 1988-08-10 1990-02-22 Philip Morris Products Inc. Fibres textile crepees et appareil presse-etoupe et procedes servant au crepage de fibres textile
US4979274A (en) * 1989-04-18 1990-12-25 The Dow Chemical Company Process and apparatus for crimping fibers

Also Published As

Publication number Publication date
EP0624666B1 (fr) 1998-01-21
DE69316592T2 (de) 1998-06-25
DE69316592D1 (de) 1998-02-26
ATE162562T1 (de) 1998-02-15

Similar Documents

Publication Publication Date Title
US5233736A (en) Apparatus and process for crimping and crosslinking fibers
US5356707A (en) Non-linear carbonaceous fiber
KR890000129B1 (ko) 스프링상 가역변형성 함탄소섬유 및 이의 제조방법
US4837076A (en) Carbonaceous fibers with spring-like reversible deflection and method of manufacture
US6375889B1 (en) Method of making machine direction stretchable nonwoven fabrics having a high degree of recovery upon elongation
US5454142A (en) Nonwoven fabric having elastometric and foam-like compressibility and resilience and process therefor
US4979274A (en) Process and apparatus for crimping fibers
US4869951A (en) Method and materials for manufacture of anti-static cloth
US3046632A (en) Method and apparatus for producing wool-like yarn from synthetic fibers
US4857404A (en) Fluorinated carbonaceous fibers
EP0624666B1 (fr) Dispositif et procédé pour le frisage et la reticulation de fibres
EP0125905B1 (fr) Procédé pour la stabilisation de fibres acryliques
US5771674A (en) Process and apparatus for crimping fibers
US4977654A (en) Process and apparatus for crimping fibers
EP0428632B1 (fr) Fibre non lineaire de polyamide aromatique ou ensemble de fibres et leur procede de preparation
US3345718A (en) Process and apparatus for texturizing textile material
US4957807A (en) Nonlinear aromatic polyamide fiber or fiber assembly
EP0336464B1 (fr) Structures en fibres de carbone densifiées
EP0507847B1 (fr) Appareil et procede pour friser des fibres
JPS62199819A (ja) 高安定性の電気抵抗率を有する部分的炭素化高分子繊維材料の製造方法
EP0506681A4 (en) Process and apparatus for crimping fibers
US4937140A (en) Fluorinated carbonaceous fibers
CA2071985A1 (fr) Appareil a friser les fibres, et methode connexe
JPH05502915A (ja) 捲縮繊維用の装置及び方法
NO123237B (fr)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IE IT LI LU MC NL PT SE

17P Request for examination filed

Effective date: 19950209

17Q First examination report despatched

Effective date: 19960722

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980121

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980121

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19980121

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980121

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980121

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980121

REF Corresponds to:

Ref document number: 162562

Country of ref document: AT

Date of ref document: 19980215

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69316592

Country of ref document: DE

Date of ref document: 19980226

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: MODIANO & ASSOCIATI S.R.L.

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980421

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980421

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980421

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980510

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980510

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: 78518

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981130

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20030519

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20030528

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20030529

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20040510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050131

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050510