WO2007041384A2 - Agent generateur de gaz - Google Patents

Agent generateur de gaz Download PDF

Info

Publication number
WO2007041384A2
WO2007041384A2 PCT/US2006/038225 US2006038225W WO2007041384A2 WO 2007041384 A2 WO2007041384 A2 WO 2007041384A2 US 2006038225 W US2006038225 W US 2006038225W WO 2007041384 A2 WO2007041384 A2 WO 2007041384A2
Authority
WO
WIPO (PCT)
Prior art keywords
gas generant
generant composition
nitrate
weight
potassium
Prior art date
Application number
PCT/US2006/038225
Other languages
English (en)
Other versions
WO2007041384A3 (fr
Inventor
Jeffrey W. Halpin
Sean P. Burns
Original Assignee
Automotive Systems Laboratory, Inc.
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 Automotive Systems Laboratory, Inc. filed Critical Automotive Systems Laboratory, Inc.
Priority to DE112006002625T priority Critical patent/DE112006002625T5/de
Priority to JP2008533715A priority patent/JP2009512613A/ja
Publication of WO2007041384A2 publication Critical patent/WO2007041384A2/fr
Publication of WO2007041384A3 publication Critical patent/WO2007041384A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/006—Stabilisers (e.g. thermal stabilisers)

Definitions

  • the present invention relates generally to gas generating systems, and to gas generant compositions employed in gas generator devices for automotive restraint systems, for example.
  • the present invention relates to gas generant compositions that upon combustion produce a relatively small amount of solids and a relatively abundant amount of gas. It is an ongoing challenge to reduce the amount of solids and increase the amount of gas thereby decreasing the filtration requirements for an inflator. As a result, the filter may be either reduced in size or eliminated altogether thereby reducing the weight and/or size of the inflator.
  • gas generant compositions that produce relatively small amounts of solids, sometimes known as "smokeless" compositions, is that not all non-metallic constituents contribute to stable ballistic performance when subjected to environmental conditioning.
  • one fuel that is favored because of its propensity to produce all or mostly gas is the mono-ammonium salt of bis-1 (2)H-tetrazol- 5-yl)-amine (BTA-1 NH3).
  • BTA-1 NH3 bis-1 (2)H-tetrazol- 5-yl)-amine
  • BTA-1 NH3 contributes to an unacceptably aggressive ballistic performance as measured after thermal cycling and thermal shock testing defined in SAE International Document SAE/USCAR-24 "USCAR INFLATOR TECHNICAL REQUIREMENTS AND VALIDATION", herein incorporated by reference.
  • compositions that contain BTA-1 NH3 that contribute to a "smokeless" gas generant composition, or one that when combusted produces 90% or more of gas as a product, while yet passing all thermal shock requirements as set forth in USCAR standards.
  • compositions including BTA-1 NH3, an oxidizer such as phase stabilized ammonium nitrate, and a fumed oxide such as fumed silica or fumed alumina. It has been found that the addition of fumed silica or fumed oxides to compositions containing BTA-1 NH3 has resulted in compositions that are now able to withstand the thermal cycling/thermal shock tests required by USCAR standards. Other constituents including processing aids such as graphite, may be included in relatively small amounts. In further accordance with the present invention, a gas generator and a vehicle occupant protection system incorporating the gas generant composition are also included.
  • FIG. 1 is a cross-sectional side view showing the general structure of an inflator in accordance with the present invention
  • FIG. 2 is a schematic representation of an exemplary vehicle occupant restraint system containing a gas generant composition in accordance with the present invention.
  • FIGS. 3 and 4 are graphical representations of a composition containing .25% by weight fumed silica.
  • FIGS. 5 and 6 are graphical representations of a composition containing .50% by weight fumed silica.
  • FIGS. 7 and 8 are graphical representations of a composition containing .75% by weight fumed silica.
  • the present invention includes gas generant compositions that in accordance with the present invention, incorporate an additive into compositions containing BTA-1 NH3 that, when added at relatively low levels, stabilizes the propellant grains when subjected to thermal cycling or thermal shock conditioning, as required for use in the automotive industry.
  • These formulations generally contain the following:
  • a first oxidizer selected from the group including nonmetal and metal nitrate salts such as ammonium nitrate, phase-stabilized ammonium nitrate, potassium nitrate, strontium nitrate; nitrite salts such as potassium nitrite; chlorate salts such as potassium chlorate; metal and nonmetal perchlorate salts such as potassium or ammonium perchlorate; oxides such as iron oxide and copper oxide; basic nitrate salts such as basic copper nitrate and basic iron nitrate; and mixtures thereof.
  • the first oxidizer is generally provided at about 0.1 -80 wt% of the gas generant composition, and more preferably at about 10-70 wt%.
  • An optional secondary oxidizer may also be provided and selected from the oxidizers described above, and when included is generally provided at about 0.1-50 wt%, and more preferably at about 0.1 -30 wt%.
  • the total oxidizer component that is the combined weight percent of all oxidizers, will nevertheless only range from 0.1 to 80 wt %.
  • a first or primary fuel consists of mono-ammonium salt of bis-(1 (2)H- tetrazol-5-yl)-amine (BTA-1 NH3) and is generally provided at about 0.1 -50 weight percent or wt%, and more preferably at about 10-30 wt%.
  • An optional secondary fuel is selected from the group containing derivatives of bis-(1 (2)H-tetrazol-5-yl)-amine, including its anhydrous acid and its acid monohydrate, from metal salts thereof including the potassium, sodium, strontium, copper, boron, zinc salts of BTA-1 NH3, and complexes thereof; azoles such as 5- aminotetrazole; metal salts of azoles such as potassium 5-aminotetrazole; nonmetal salts of azoles such as mono-or di-ammonium salt of 5, 5'-bis-1 H-tetrazole; nitrate salts of azoles such as 5-aminotetrazole nitrate; nitramine derivatives of azoles such as 5- nitraminotetrazole; metal salts of nitramine derivatives of azoles such as di-potassium 5- nitraminotetrazole; nonmetal salts of nitramine derivatives of azoles such as mono- or di- ammonium
  • a first or primary additive is selected from the group of fumed metal oxides including fumed silica and fumed alumina, and mixtures thereof, and is generally provided at about 0.05-10 wt%, and more preferably at about 0.05-5 wt%. All percentages for the constituents described herein are presented as weight percents of a total gas generant weight.
  • An optional second additive is selected from the group including silicon compounds including elemental silicon, silicon dioxide, and fused silica; silicones such as polydimethylsiloxane; silicates such as potassium silicates; natural minerals such as talc, mica, and clay; lubricants such as graphite powder or fibers, magnesium stearate, boron nitride, molybdenum sulfide; and mixtures thereof, and when included is generally provided at about 0.1 -10%, and more preferably at about 0.1 -5%.
  • silicones such as polydimethylsiloxane
  • silicates such as potassium silicates
  • natural minerals such as talc, mica, and clay
  • lubricants such as graphite powder or fibers, magnesium stearate, boron nitride, molybdenum sulfide; and mixtures thereof, and when included is generally provided at about 0.1 -10%, and more preferably at about 0.1 -5%.
  • An optional binder is selected from the group of cellulose derivatives such as cellulose acetate, cellulose acetate butyrate, carboxymethycellulose, salts of carboxymethylcellulose, carboxymethylcellulose acetate butyrate; silicone; polyalkene carbonates such as polypropylene carbonate and polyethylene carbonate; and mixtures thereof, and when included is generally provided at about 0.1-10%, and more preferably at about 0.1 -5%. All percentages for the constituents described herein are presented as weight percents of the total gas generant weight.
  • BTA-1 NH3 When combined with PSAN, exhibits many favorable qualities for use in automotive passenger restraints, and therefore forms preferred gas generating compositions.
  • BTA-1 NH3 is a high energy, high-nitrogen fuel which exhibits excellent stability and very favorable levels of hygroscopicity and sensitivity.
  • PSAN more specifically, exhibits no sensitivity when subjected to impact, friction, or electrostatic discharge stimuli. Dry mixes of formulations containing these materials were made. The raw materials were ground together for 15 minutes in a Sweco vibratory mill.
  • a smokeless gas generant was produced by mixing Phase-Stabilized Ammonium Nitrate (PSAN) containing 10% by weight Potassium Nitrate, with bis-(1 (2)H-tetrazol-5-yl)- amine, mono-ammonium salt (BTA-1 NH3). The mixture was substantially in stoichiometric balance. The components were ground dry for about 15 minutes within a Sweco Vibratory Jar Mill.
  • PSAN Phase-Stabilized Ammonium Nitrate
  • BTA-1 NH3 bis-(1 (2)H-tetrazol-5-yl)- amine, mono-ammonium salt
  • fumed silica was commercially available as M-5 Grade provided by Cabot Corporation. Initially, the fumed silica was added at levels between about 3-6% by mass. The stoichiometric balance of the fuel and oxidizer and processing were kept the same. The resultant gas generants were then ballistically evaluated via the same method described above. After thermal shock conditioning, no change had occurred in the ballistic performance. However, the addition of such a large amount of "inert" material detracted from or inhibited the energy of the system and therefore made the formulations not as desirable.
  • the ballistic data for the mixture containing 0.25% silica is illustrated in Figures 3 and 4.
  • the pressure was measured inside the inflator and inside a 60-L tank during deployment prior to thermal shock tests and is represented in Figure 3.
  • Figure 4 illustrates the results of combusting this mixture after thermal shock testing where a spike in the pressure indicates excessively aggressive ballistic performance.
  • One of the thermal shock inflator pressures actually increased high enough to fracture the inflator body. These results are unfavorable for use in the automotive industry.
  • a few tablets were weighed and measured to determine density both before and after thermal shock conditioning. The crush strength was also measured for comparison. This data is shown in Table 1 .
  • the ballistic data for the mixture containing 0.5% silica can be seen in Figures 5 and 6.
  • the pressure was measured inside the inflator and inside a 60-L tank during deployment prior to thermal shock tests and is represented in Figure 5.
  • Figure 6 illustrates the results of combusting this mixture after thermal shock testing wherein the pressure curves indicate excessively aggressive ballistic performance.
  • the pressure was measured inside the inflator and inside a 60-L tank during deployment.
  • the data from the thermal shock inflators showed an improvement over the mixture containing 0.25% silica. This improvement, however, was not sufficient to make the inflators viable for use according to the USCAR specification.
  • a few tablets were weighed and measured to determine density both before and after thermal shock conditioning. The crush strength was also measured for comparison. This data is shown in Table 1 .
  • the ballistic data for the mixture containing 0.75% silica can be seen in Figures 7 and 8.
  • the pressure was measured inside the inflator and inside a 60-L tank during deployment prior to thermal shock tests and is represented in Figure 7.
  • Figure 8 illustrates the results of combusting this mixture after thermal shock testing wherein the pressure indicates consistent ballistic performance before and after thermal shock.
  • the pressure was measured inside the inflator and inside the 60-L tank during deployment.
  • the data from the thermal shock inflators again showed an improvement over the mixture containing 0.5% silica.
  • the ballistic performance after thermal shock indicates a minimal change. Analysis of this data determined these inflators acceptable according to the USCAR specification. A few tablets were weighed and measured to determine density both before and after thermal shock conditioning. The crush strength was also measured for comparison. This data can be seen in Table 1 .
  • an exemplary inflator incorporates a dual chamber design to tailor the force of deployment an associated airbag.
  • an inflator containing a primary gas generant 1 2 formed as described herein may be manufactured as known in the art.
  • U.S. Patent IMos. 6,422,601 , 6,805,377, 6,659,500, 6,749,219, and 6,752,421 exemplify typical airbag inflator designs and are each incorporated herein by reference in their entirety.
  • the exemplary inflator 10 described above may also be incorporated into a gas generating system or airbag system 200.
  • Airbag system 200 includes at least one airbag 202 and an inflator 10 containing a gas generant composition 12 in accordance with the present invention, coupled to airbag 202 so as to enable fluid communication with an interior of the airbag.
  • Airbag system 200 may also include (or be in communication with) a crash event sensor 210.
  • Crash event sensor 210 includes a known crash sensor algorithm that signals actuation of airbag system 200 via, for example, activation of airbag inflator 10 in the event of a collision.
  • FIG. 2 shows a schematic diagram of one exemplary embodiment of such a restraint system.
  • Safety belt assembly 150 includes a safety belt housing 152 and a safety belt 100 extending from housing 152.
  • a safety belt retractor mechanism 1 54 (for example, a spring-loaded mechanism) may be coupled to an end portion of the belt.
  • a safety belt pretensioner 156 containing propellant 12 and autoignition 14 may be coupled to belt retractor mechanism 154 to actuate the retractor mechanism in the event of a collision.
  • Typical seat belt retractor mechanisms which may be used in conjunction with the safety belt embodiments of the present invention are described in U.S. Pat. Nos. 5,743,480, 5,553,803, 5,667,161 , 5,451 ,008, 4,558,832 and 4,597,546, incorporated herein by reference.
  • Illustrative examples of typical pretensioners with which the safety belt embodiments of the present invention may be combined are described in U.S. Pat. Nos. 6,505,790 and 6,419,177, incorporated herein by reference.
  • Safety belt assembly 150 may also include (or be in communication with) a crash event sensor 158 (for example, an inertia sensor or an accelerometer) including a known crash sensor algorithm that signals actuation of belt pretensioner 156 via, for example, activation of a pyrotechnic igniter (not shown) incorporated into the pretensioner.
  • a crash event sensor 158 for example, an inertia sensor or an accelerometer
  • U.S. Pat. Nos. 6,505,790 and 6,419,177 previously incorporated herein by reference, provide illustrative examples of pretensioners actuated in such a manner.
  • safety belt assembly 150 airbag system 200, and more broadly, vehicle occupant protection system 180 exemplify but do not limit gas generating systems contemplated in accordance with the present invention.
  • vehicle occupant protection system 180 exemplify but do not limit gas generating systems contemplated in accordance with the present invention.
  • the compositions described above do not limit the present invention. It should be understood that the preceding is merely a detailed description of various embodiments of this invention and that numerous changes to the disclosed embodiments can be made in accordance with the disclosure herein without departing from the scope of the invention. The preceding description, therefore, is not meant to limit the scope of the invention. Rather, the scope of the invention is to be determined only by the appended claims and their equivalents.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Air Bags (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)

Abstract

L'invention concerne des compositions génératrices de gaz contenant un sel mono-ammonium de bis (1 (2) H-tétrazol-5-yl)-amine, un oxydant tel qu'un nitrate d'ammonium à phase stabilisée, et un premier additif choisi parmi les oxydes sublimés tels que la silice sublimée. L'invention concerne également des dispositifs (10) générateurs de gaz et des systèmes (200) générateurs de gaz contenant ces compositions.
PCT/US2006/038225 2005-09-29 2006-09-29 Agent generateur de gaz WO2007041384A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE112006002625T DE112006002625T5 (de) 2005-09-29 2006-09-29 Gaserzeugungsmittel
JP2008533715A JP2009512613A (ja) 2005-09-29 2006-09-29 ガス生成物質

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US72187305P 2005-09-29 2005-09-29
US60/721,873 2005-09-29
US11/540,841 US20070084531A1 (en) 2005-09-29 2006-09-29 Gas generant

Publications (2)

Publication Number Publication Date
WO2007041384A2 true WO2007041384A2 (fr) 2007-04-12
WO2007041384A3 WO2007041384A3 (fr) 2007-11-22

Family

ID=37947061

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2006/038225 WO2007041384A2 (fr) 2005-09-29 2006-09-29 Agent generateur de gaz

Country Status (3)

Country Link
US (1) US20070084531A1 (fr)
JP (1) JP2009512613A (fr)
WO (1) WO2007041384A2 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070169863A1 (en) * 2006-01-19 2007-07-26 Hordos Deborah L Autoignition main gas generant
US20100326575A1 (en) * 2006-01-27 2010-12-30 Miller Cory G Synthesis of 2-nitroimino-5-nitrohexahydro-1,3,5-triazine
US7959749B2 (en) * 2006-01-31 2011-06-14 Tk Holdings, Inc. Gas generating composition
US7758709B2 (en) * 2006-06-21 2010-07-20 Autoliv Asp, Inc. Monolithic gas generant grains
US20080271825A1 (en) * 2006-09-29 2008-11-06 Halpin Jeffrey W Gas generant
US7714143B1 (en) * 2007-03-31 2010-05-11 Tk Holdings, Inc. Method of making monoammonium salt of 5,5′-bis-1H-tetrazole
US9556078B1 (en) 2008-04-07 2017-01-31 Tk Holdings Inc. Gas generator
US8815029B2 (en) * 2008-04-10 2014-08-26 Autoliv Asp, Inc. High performance gas generating compositions
US8808476B2 (en) * 2008-11-12 2014-08-19 Autoliv Asp, Inc. Gas generating compositions having glass fibers
US20100261912A1 (en) * 2009-02-17 2010-10-14 Toshiyuki Toda Bis-(1(2)h-tetrazol-5-yl)amine and production method therefor
US9051223B2 (en) 2013-03-15 2015-06-09 Autoliv Asp, Inc. Generant grain assembly formed of multiple symmetric pieces
CN107698414B (zh) * 2017-10-24 2019-08-09 湖北航鹏化学动力科技有限责任公司 气体发生剂组合物、制备方法、应用及气体发生器

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040016480A1 (en) * 2002-04-04 2004-01-29 Williams Graylon K. Nonazide gas generant compositions
US20050067074A1 (en) * 1994-01-19 2005-03-31 Hinshaw Jerald C. Metal complexes for use as gas generants

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US503575A (en) * 1893-08-22 Charles elis bratt
US5139588A (en) * 1990-10-23 1992-08-18 Automotive Systems Laboratory, Inc. Composition for controlling oxides of nitrogen
US5084118A (en) * 1990-10-23 1992-01-28 Automotive Systems Laboratory, Inc. Ignition composition for inflator gas generators
JP3189990B2 (ja) * 1991-09-27 2001-07-16 キヤノン株式会社 電子回路装置
US5783773A (en) * 1992-04-13 1998-07-21 Automotive Systems Laboratory Inc. Low-residue azide-free gas generant composition
US5386775A (en) * 1993-06-22 1995-02-07 Automotive Systems Laboratory, Inc. Azide-free gas generant compositions and processes
US5380380A (en) * 1994-02-09 1995-01-10 Automotive Systems Laboratory, Inc. Ignition compositions for inflator gas generators
US5538567A (en) * 1994-03-18 1996-07-23 Olin Corporation Gas generating propellant
CA2162391C (fr) * 1994-04-04 2003-05-13 Automotive Systems Laboratory, Inc. Compositions inflammables pour generateurs de gaz de gonflage
US5460668A (en) * 1994-07-11 1995-10-24 Automotive Systems Laboratory, Inc. Nonazide gas generating compositions with reduced toxicity upon combustion
US5533941A (en) * 1995-02-16 1996-07-09 Belting Industries Co., Inc. Belt and method of manufacture
US5545272A (en) * 1995-03-03 1996-08-13 Olin Corporation Thermally stable gas generating composition
US5514230A (en) * 1995-04-14 1996-05-07 Automotive Systems Laboratory, Inc. Nonazide gas generating compositions with a built-in catalyst
US5756929A (en) * 1996-02-14 1998-05-26 Automotive Systems Laboratory Inc. Nonazide gas generating compositions
US6306232B1 (en) * 1996-07-29 2001-10-23 Automotive Systems Laboratory, Inc. Thermally stable nonazide automotive airbag propellants
US6007647A (en) * 1996-08-16 1999-12-28 Automotive Systems Laboratory, Inc. Autoignition compositions for inflator gas generators
US5872329A (en) * 1996-11-08 1999-02-16 Automotive Systems Laboratory, Inc. Nonazide gas generant compositions
US6074502A (en) * 1996-11-08 2000-06-13 Automotive Systems Laboratory, Inc. Smokeless gas generant compositions
US6077371A (en) * 1997-02-10 2000-06-20 Automotive Systems Laboratory, Inc. Gas generants comprising transition metal nitrite complexes
US5962808A (en) * 1997-03-05 1999-10-05 Automotive Systems Laboratory, Inc. Gas generant complex oxidizers
US6287400B1 (en) * 1999-03-01 2001-09-11 Automotive Systems Laboratory, Inc. Gas generant composition
US6475312B1 (en) * 1999-04-07 2002-11-05 Automotive Systems Laboratory, Inc. Method of formulating a gas generant composition
JP2003535003A (ja) * 1999-07-02 2003-11-25 オートモーティブ システムズ ラボラトリー インコーポレーテッド シリコーン被膜を含むガス発生組成物
WO2002043990A2 (fr) * 2000-11-28 2002-06-06 Automotive Systems Laboratory, Inc. Générateur de gaz et procédé d'assemblage
US7097296B2 (en) * 2003-04-21 2006-08-29 Roszak Amy C Composition for printing on vellum and the like

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050067074A1 (en) * 1994-01-19 2005-03-31 Hinshaw Jerald C. Metal complexes for use as gas generants
US20040016480A1 (en) * 2002-04-04 2004-01-29 Williams Graylon K. Nonazide gas generant compositions

Also Published As

Publication number Publication date
JP2009512613A (ja) 2009-03-26
US20070084531A1 (en) 2007-04-19
WO2007041384A3 (fr) 2007-11-22

Similar Documents

Publication Publication Date Title
US20070084531A1 (en) Gas generant
US20080271825A1 (en) Gas generant
US6210505B1 (en) High gas yield non-azide gas generants
US20070084532A1 (en) Gas generant
US20030145923A1 (en) Propellant for gas generators
US20060219340A1 (en) Gas generating system
US20090020197A1 (en) Gas generating compositions and airbag inflators
US20110169254A1 (en) Active-active failover for a direct-attached storage system
EP2690081B1 (fr) Composition d'agent générateur de gaz
WO2005094366A2 (fr) Systeme generateur de gaz
US10358393B2 (en) Gas generating compositions and methods of making and using thereof
JP6560476B1 (ja) 改善されたブースター組成物
US20070277915A1 (en) Gas generant compositions
US8002915B2 (en) Gas generant compositions
EP1513785B1 (fr) Composition génératrice de gaz
US20090008003A1 (en) Gas generant
US7879167B2 (en) Gas generating composition
USRE44721E1 (en) Method of making monoammonium salt of bis-(1(2)H-tetrazol-5-yl)-amine
US20230219866A1 (en) Gas generating compositions and methods of using
WO1999046222A2 (fr) Substances generatrices de gaz exempts d'azotures et possedant un rendement eleve
CA2260144C (fr) Gaz propulseurs thermostables non-azide pour coussins gonflables de securite pour automobiles
CN114988974A (zh) 改进的增压组合物
DE112006002625T5 (de) Gaserzeugungsmittel

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2008533715

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1120060026259

Country of ref document: DE

RET De translation (de og part 6b)

Ref document number: 112006002625

Country of ref document: DE

Date of ref document: 20080828

Kind code of ref document: P

122 Ep: pct application non-entry in european phase

Ref document number: 06804276

Country of ref document: EP

Kind code of ref document: A2