[go: up one dir, main page]

WO2015084553A1 - Acrylic adhesive compositions, manufacture and use thereof - Google Patents

Acrylic adhesive compositions, manufacture and use thereof Download PDF

Info

Publication number
WO2015084553A1
WO2015084553A1 PCT/US2014/065179 US2014065179W WO2015084553A1 WO 2015084553 A1 WO2015084553 A1 WO 2015084553A1 US 2014065179 W US2014065179 W US 2014065179W WO 2015084553 A1 WO2015084553 A1 WO 2015084553A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
toluidine
acrylic adhesive
available
adhesive composition
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.)
Ceased
Application number
PCT/US2014/065179
Other languages
French (fr)
Inventor
Gary L. Jialanella
Eric E. Cole
Andreas Lutz
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.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
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 Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of WO2015084553A1 publication Critical patent/WO2015084553A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used

Definitions

  • the present invention relates to a new adhesive composition having unique properties in some automotive related applications.
  • Rapid curing adhesive compositions are becoming more critical for bonding closure panels (doors, hoods, etc.) by the automotive OEMs. Because of this, many adhesive suppliers have used acrylic chemistry to accelerate cure time. However, acrylic adhesives typically can't resist the high temperatures associated with e-coat ovens in the automotive industry so some specific amount of epoxy chemistry is required. The rapid cure requirement is related to handling strength prior to final cure in the oven, and the type of cure accelerators for the acrylic adhesive composition is crucial. There are two typical systems used to cure acrylic adhesives: metal ester/hydroperoxide or tertiary amine (N,N- dialkyl substituted toluidine)/benzoyl peroxide. Both of these systems are quite slow when used without a co-catalyst. The most common co-catalysts or accelerators are hydrazines, sulfimides or quinolines.
  • the present invention provides the use of dihydroxyl substituted toluidines as catalysts which don't require the use of co-catalysts or co-accelerators for rapid cure rate of acrylic adhesives.
  • the present invention also provides a composition that contains a hexafunctional urethane acrylate.
  • Figure 1 illustrates the cure profile comparison of the present adhesive comprising dihydroxyethyl toluidine vs. prior art adhesives comprising dimethyl toluidine.
  • the present invention provides an adhesive composition that contains liquid epoxy resin; a styrene-butadiene-styrene copolymer and a methacrylate terminated butadiene - acrylonitrile copolymer; a dihydroxy substituted toluidine; and a hardener.
  • the composition contains about 40 to 50 wt , preferably about 44.5 wt. of a liquid epoxy resin.
  • the wt.% is based on the total weight of the composition.
  • liquid epoxy resins examples include bisphenol-A such as DERTM 331 available from The Dow Chemical Company.
  • Other liquid epoxy resins such as EPON 828 available from Momentive may also be used in the similar amounts.
  • the composition contains about 15 to 20 wt.%, preferably about 18 wt.%, based on the total weight of the composition, of a styrene-butadiene-styrene copolymer and a methacrylate terminated butadiene-acrylonitrile copolymer.
  • the weight ratio between these two copolymers can be 2:1 to 1:2 but preferable 1:2.
  • Examples of styrene-butadiene- styrene copolymer include VectorTM 2518 available from Dexco Polymers and examples of methacrylate terminated butadiene-acrylonitrile copolymer include HycarTM 1300X333 available from Emerald Chemical.
  • composition of the present invention also contain about 2 to 3 wt%, preferably
  • composition of the present invention may also contain about 7 to 8 wt.%, preferably, 7.5wt.%, based on the total weight of the composition, of a toughener such as acrylic core shell rubber and other conventionally used tougheners.
  • a toughener such as acrylic core shell rubber and other conventionally used tougheners.
  • the composition may also contain about 0.6 to 0.7 wt.%, preferably, 0.65 wt.%, of a benzoyl peroxide; about 16 to 18 wt%, preferably 17 wt.% of a methyl methacrylate; and about 1 to 3 wt.%, preferably 2 wt.% of a methacrylic acid.
  • the adhesive composition of the present invention also contains a hexafunctional urethane acrylate.
  • the hexafunctional urethane acrylate is used to significantly increase the apparent cure rate. It accomplishes this effect by increasing the crosslink density early in the reaction.
  • the composition may contain 0.25 to 0.75 wt%, preferably 0.5 wt%, based on total weight of the composition, of such a hexafunctional urethane acrylate.
  • Examples of commercial hexafunctional urethane acrylates include CN 975 available from Sartomer.
  • a conventional mixing process may be used to prepare the present adhesive composition. The components may be mixed in any order.
  • Benzoyl peroxide (LuperoxTM AFR40, 40% BPO in plasticizer) available from Arkema
  • compositions Two samples of compositions were prepared with one sample containing dihyroxy ethyl toluidine (Example 1) and another one containing dimethyl toluidine (Example 2) as a comparative sample. All compositions were mixed using a dual asymmetric centrifugal FlackTek SpeedMixer ® DAC 400 FVZ by Hauschild Engineering. All rubbers were first dissolved in monomer or epoxy resin by mixing the speed mixer cup on the speed mixer for two minutes cycles at a speed of 2,200 rpm. The temperature of the samples was checked after the two minute mix using an infrared temperature probe and visually evaluated for homogeneity. If the sample was not visually homogeneous, additional two minute 2,200 rpm mixing cycles were utilized until visual homogeneity was achieved. The remaining ingredients were added to the formulation and mixed for two minutes cycles at a speed of 2,200 rpm. The peroxide was added after the sample had cooled below 40°C and mixed for 1 minute at 2,200 rpm.
  • Each composition contains two separately made components (A side and B side).
  • the two components of the adhesive were combined in a 1 : 1 ratio by weight and mixed by hand in a bag for 1 minute.
  • Example 1 Adhesive composition with dihydroxyethyl toluidine
  • the two prepared adhesive compositions were separately dispensed on a 25 mm disposable plate connected to a TA Instruments AR-2000EX Reheometer.
  • the gap between the plates was set to 1 ,050 ⁇ and the excess adhesive that was squeezed out was scraped away using a spatula.
  • the gap was then lowered to 1,000 ⁇ to ensure that a consistent sample volume was used for each measurement.
  • An oscillatory time sweep was performed at a constant strain of 0.1% strain at a Frequency of 1 Hz to monitor the storage modulus (G') as a function of cure time.
  • T-Peel samples were prepared by bending 1 inch by 4 inch metal strips at a 90° angle yielding a 3 inch bonding section.
  • the substrate was wiped with acetone.
  • the adhesive composition was then applied to one strip and 10 mil glass bead spacers were sprinkled on the adhesive.
  • a second strip was placed on the adhesive to create the T-Peel joint assembly.
  • the assembly was held with clips and cured at room temperature and in an oven set to 170°C for the times indicated in Table 1. After curing, the samples were tested on an Instron to develop a load cure. The average load was taken to give the pounds of force per linear inch of substrate.
  • T-peel strengths The fully cured properties of both adhesive compositions, as measured by T-peel strengths, are shown in Table 1. The T-peel strengths are the same regardless of the cure profile.
  • CRS stands for cold rolled steel
  • HDG stands for hot dipped galvanized steel

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to an adhesive composition comprising a dihydroxy substituted toluidine and a hexafunctional urethane acrylate.

Description

ACRYLIC ADHESIVE COMPOSITIONS, MANUFACTURE AND USE THEREOF
FIELD OF THE INVENTION
The present invention relates to a new adhesive composition having unique properties in some automotive related applications. INTRODUCTION
Rapid curing adhesive compositions are becoming more critical for bonding closure panels (doors, hoods, etc.) by the automotive OEMs. Because of this, many adhesive suppliers have used acrylic chemistry to accelerate cure time. However, acrylic adhesives typically can't resist the high temperatures associated with e-coat ovens in the automotive industry so some specific amount of epoxy chemistry is required. The rapid cure requirement is related to handling strength prior to final cure in the oven, and the type of cure accelerators for the acrylic adhesive composition is crucial. There are two typical systems used to cure acrylic adhesives: metal ester/hydroperoxide or tertiary amine (N,N- dialkyl substituted toluidine)/benzoyl peroxide. Both of these systems are quite slow when used without a co-catalyst. The most common co-catalysts or accelerators are hydrazines, sulfimides or quinolines.
The present invention provides the use of dihydroxyl substituted toluidines as catalysts which don't require the use of co-catalysts or co-accelerators for rapid cure rate of acrylic adhesives. The present invention also provides a composition that contains a hexafunctional urethane acrylate.
BRIEF DESCRIPTION OF DRAWINGS
Figure 1 illustrates the cure profile comparison of the present adhesive comprising dihydroxyethyl toluidine vs. prior art adhesives comprising dimethyl toluidine.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides an adhesive composition that contains liquid epoxy resin; a styrene-butadiene-styrene copolymer and a methacrylate terminated butadiene - acrylonitrile copolymer; a dihydroxy substituted toluidine; and a hardener.
Typically, the composition contains about 40 to 50 wt , preferably about 44.5 wt. of a liquid epoxy resin. The wt.% is based on the total weight of the composition.
Examples of liquid epoxy resins include bisphenol-A such as DER™ 331 available from The Dow Chemical Company. Other liquid epoxy resins such as EPON 828 available from Momentive may also be used in the similar amounts.
The composition contains about 15 to 20 wt.%, preferably about 18 wt.%, based on the total weight of the composition, of a styrene-butadiene-styrene copolymer and a methacrylate terminated butadiene-acrylonitrile copolymer. The weight ratio between these two copolymers can be 2:1 to 1:2 but preferable 1:2. Examples of styrene-butadiene- styrene copolymer include Vector™ 2518 available from Dexco Polymers and examples of methacrylate terminated butadiene-acrylonitrile copolymer include Hycar™ 1300X333 available from Emerald Chemical.
The composition of the present invention also contain about 2 to 3 wt%, preferably
2.25 wt.%, based on the total weight of the composition , of a dihydroxy substituted toluidine. A preferred dihydroxy substituted toluidine used in the present invention is N,N- dihydroxyethyl-p-toluidine, available as X-866-000 from ESSTECH, INC. Other dihydroxy substituted toluidine may include dihydroxy ethyl or dihydroxy propyl. In addition to above, the composition of the present invention may also contain about 7 to 8 wt.%, preferably, 7.5wt.%, based on the total weight of the composition, of a toughener such as acrylic core shell rubber and other conventionally used tougheners.
In some preferred embodiments of the present invention, the composition may also contain about 0.6 to 0.7 wt.%, preferably, 0.65 wt.%, of a benzoyl peroxide; about 16 to 18 wt%, preferably 17 wt.% of a methyl methacrylate; and about 1 to 3 wt.%, preferably 2 wt.% of a methacrylic acid.
Other typical components of an adhesive composition, such as curing agent, fillers etc, may also be used.
In a preferred embodiment, the adhesive composition of the present invention also contains a hexafunctional urethane acrylate. The hexafunctional urethane acrylate is used to significantly increase the apparent cure rate. It accomplishes this effect by increasing the crosslink density early in the reaction. The composition may contain 0.25 to 0.75 wt%, preferably 0.5 wt%, based on total weight of the composition, of such a hexafunctional urethane acrylate. Examples of commercial hexafunctional urethane acrylates include CN 975 available from Sartomer. A conventional mixing process may be used to prepare the present adhesive composition. The components may be mixed in any order.
The present invention can be further illustrated with the following non- limiting examples:
Sources of raw materials:
DER™ 331 - liquid bisphenol-A epoxy resin available from The Dow Chemical Company
Benzoyl peroxide (Luperox™ AFR40, 40% BPO in plasticizer) available from Arkema
Hycar™ 1300X333 - (methacrylate terminated butadiene-acrylonitrile copolymer) available from Emerald Chemical
Paraloid™ BTA 753 - acrylic core shell rubber available from The Dow Chemical Company.
CN 975 - hexafunctional urethane acrylate available from Sartomer
Cab-O-Sil™ - hydrophobic fumed silica available from Cabot
Butylated hydroxyl tolene - available from Sigma Aldrich
Methyl methacrylate - available from Sigma Aldrich
Methacrylic acid - available from Sigma Aldrich
Amicure™ CD- 1200 - dicyandiamide available from Air Products
Omnicure™ U-405 - phenyl dimethyl urea available from CVC Chemicals
Preparation of Examples
Two samples of compositions were prepared with one sample containing dihyroxy ethyl toluidine (Example 1) and another one containing dimethyl toluidine (Example 2) as a comparative sample. All compositions were mixed using a dual asymmetric centrifugal FlackTek SpeedMixer® DAC 400 FVZ by Hauschild Engineering. All rubbers were first dissolved in monomer or epoxy resin by mixing the speed mixer cup on the speed mixer for two minutes cycles at a speed of 2,200 rpm. The temperature of the samples was checked after the two minute mix using an infrared temperature probe and visually evaluated for homogeneity. If the sample was not visually homogeneous, additional two minute 2,200 rpm mixing cycles were utilized until visual homogeneity was achieved. The remaining ingredients were added to the formulation and mixed for two minutes cycles at a speed of 2,200 rpm. The peroxide was added after the sample had cooled below 40°C and mixed for 1 minute at 2,200 rpm.
Details of the components in each of the two Examples are listed below. Each composition contains two separately made components (A side and B side). The two components of the adhesive were combined in a 1 : 1 ratio by weight and mixed by hand in a bag for 1 minute.
Example 1 : Adhesive composition with dihydroxyethyl toluidine
Epoxy Acrylic A Side,
Weight
Figure imgf000005_0001
Example 2: Adhesive composition with dimethyl toluidine
Epoxy Acrylic A Side,
Weight
Figure imgf000006_0001
Testing Procedures and Results
1. Cure Profile
The two prepared adhesive compositions were separately dispensed on a 25 mm disposable plate connected to a TA Instruments AR-2000EX Reheometer. The gap between the plates was set to 1 ,050 μ and the excess adhesive that was squeezed out was scraped away using a spatula. The gap was then lowered to 1,000 μ to ensure that a consistent sample volume was used for each measurement. An oscillatory time sweep was performed at a constant strain of 0.1% strain at a Frequency of 1 Hz to monitor the storage modulus (G') as a function of cure time.
The results were plotted in Figure 1. As can be shown in Figure 1, the cure rate of the composition, as measured by G', is greatly enhanced when the hydroxyl ethyl toluidine is used as the peroxide activator in the composition. When the conventional activator is used in the composition, e.g. N,N-dimethyl-p-toluidine, the cure rate is much slower.
2. T-Peel
T-Peel samples were prepared by bending 1 inch by 4 inch metal strips at a 90° angle yielding a 3 inch bonding section. The substrate was wiped with acetone. The adhesive composition was then applied to one strip and 10 mil glass bead spacers were sprinkled on the adhesive. A second strip was placed on the adhesive to create the T-Peel joint assembly. The assembly was held with clips and cured at room temperature and in an oven set to 170°C for the times indicated in Table 1. After curing, the samples were tested on an Instron to develop a load cure. The average load was taken to give the pounds of force per linear inch of substrate.
The fully cured properties of both adhesive compositions, as measured by T-peel strengths, are shown in Table 1. The T-peel strengths are the same regardless of the cure profile.
Table 1 : T-Peel Results
Figure imgf000008_0001
CRS stands for cold rolled steel
HDG stands for hot dipped galvanized steel
CF means cohesive failure
AF means adhesive failure
RT stands for room temperature

Claims

CLAIMS:
An acrylic adhesive composition comprising
a) liquid epoxy resin;
b) a styrene-butadiene-styrene copolymer and a methacrylate terminated butadiene- acrylonitrile copolymer;
c) a dihydroxy substituted toluidine; and
d) a hardener.
The composition of claim 1 further comprising
e) benzoyl peroxide
f) methyl methacrylate
g) methacrylic Acid.
3. The acrylic adhesive composition of claim 1 further comprising a hexafunctional urethane acrylate.
4. The acrylic adhesive composition of any one of the previous claims wherein the dihyroxy substituted toluidine is N,N-dihydroxyethyl-p-Toluidine.
PCT/US2014/065179 2013-12-05 2014-11-12 Acrylic adhesive compositions, manufacture and use thereof Ceased WO2015084553A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361912045P 2013-12-05 2013-12-05
US61/912,045 2013-12-05

Publications (1)

Publication Number Publication Date
WO2015084553A1 true WO2015084553A1 (en) 2015-06-11

Family

ID=52117972

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2014/065179 Ceased WO2015084553A1 (en) 2013-12-05 2014-11-12 Acrylic adhesive compositions, manufacture and use thereof

Country Status (1)

Country Link
WO (1) WO2015084553A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018169609A1 (en) * 2017-03-17 2018-09-20 Dow Global Technologies Llc Epoxy-acrylic hybrid adhesive
KR20180122190A (en) * 2017-05-02 2018-11-12 주식회사 엘지화학 Two part adhecive composition
WO2024075480A1 (en) * 2022-10-04 2024-04-11 三菱瓦斯化学株式会社 Thermosetting resin composition, cured product of same, prepreg, fiber-reinforced composite material, and high-pressure gas container

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020117259A1 (en) * 2000-12-11 2002-08-29 Giroux Donald J. Two part, room temperature curable epoxy resin/ (meth) acrylate compositions with high flash point and low odor, reaction products of which demonstrate improved fixture
US20040118514A1 (en) * 2002-12-19 2004-06-24 Gosiewski Donald E. Heat resistant, impact resistant, acrylic/epoxy adhesives
US20110313082A1 (en) * 2009-02-25 2011-12-22 Matthias Popp Epoxy adhesive compositions with high mechanical strength over a wide temperature range
WO2013074265A1 (en) * 2011-11-14 2013-05-23 Henkel Corporation Adhesive compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020117259A1 (en) * 2000-12-11 2002-08-29 Giroux Donald J. Two part, room temperature curable epoxy resin/ (meth) acrylate compositions with high flash point and low odor, reaction products of which demonstrate improved fixture
US20040118514A1 (en) * 2002-12-19 2004-06-24 Gosiewski Donald E. Heat resistant, impact resistant, acrylic/epoxy adhesives
US20110313082A1 (en) * 2009-02-25 2011-12-22 Matthias Popp Epoxy adhesive compositions with high mechanical strength over a wide temperature range
WO2013074265A1 (en) * 2011-11-14 2013-05-23 Henkel Corporation Adhesive compositions

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018169609A1 (en) * 2017-03-17 2018-09-20 Dow Global Technologies Llc Epoxy-acrylic hybrid adhesive
CN110352225A (en) * 2017-03-17 2019-10-18 陶氏环球技术有限责任公司 Epoxy acrylic mixing adhesive
JP2020510731A (en) * 2017-03-17 2020-04-09 ダウ グローバル テクノロジーズ エルエルシー Epoxy-acrylic hybrid adhesive
CN110352225B (en) * 2017-03-17 2021-07-30 陶氏环球技术有限责任公司 Epoxy Acrylic Hybrid Adhesive
US11186756B2 (en) 2017-03-17 2021-11-30 Ddp Specialty Electronic Materials Us, Llc Epoxy-acrylic hybrid adhesive
JP7028884B2 (en) 2017-03-17 2022-03-02 ダウ グローバル テクノロジーズ エルエルシー Epoxy-acrylic hybrid adhesive
KR20180122190A (en) * 2017-05-02 2018-11-12 주식회사 엘지화학 Two part adhecive composition
KR102327704B1 (en) 2017-05-02 2021-11-16 주식회사 엘지화학 Two part adhecive composition
WO2024075480A1 (en) * 2022-10-04 2024-04-11 三菱瓦斯化学株式会社 Thermosetting resin composition, cured product of same, prepreg, fiber-reinforced composite material, and high-pressure gas container

Similar Documents

Publication Publication Date Title
CA2950131C (en) Heat and moisture resistant acrylic adhesive composition
JPH02178374A (en) Two-part liquid type acrylic adhesion composition
CN106661409B (en) Priming paint for adhesive tape
WO2017082106A1 (en) Bonding method, bonded structure and bonding kit
JP6662376B2 (en) Reactive hot melt adhesive composition
BR112015020062B1 (en) TWO-PART ADHESIVE FORMULATIONS AND PROCESS OF APPLYING AN ADHESIVE TO A SUBSTRATE
WO2015084553A1 (en) Acrylic adhesive compositions, manufacture and use thereof
CN110088193B (en) Composition comprising a metal oxide and a metal oxide
JPH0339116B2 (en)
JP2020526637A (en) 1-agent type thermosetting acrylate adhesive precursor and its preparation method
JP2018168227A (en) Adhesive composition and method for producing the same
JPS5925855A (en) Adhesive composition
AU2009325024B2 (en) Peroxide dispersions
JP6386969B2 (en) Acrylic resin for adhesive and acrylic resin composition for adhesive containing the same
JP2019172744A (en) Manufacturing method of bonding structure
JP2757217B2 (en) Adhesive composition
JP2020026507A (en) Two-part acrylic adhesive composition, joined body joined thereby
EP4334368A1 (en) Two-part curable composition
JP2757216B2 (en) Adhesive composition
KR101168956B1 (en) Primer for impact absorption rubber gel without pre-treatment process
CN112646536B (en) Two-component acrylic structural adhesive for metal oil surface bonding
JP7611730B2 (en) Two-component adhesive composition
SG190605A1 (en) Solution polymerization process and adhesive, sealant, and mastic compositions made therefrom
JPH09183950A (en) Two-component acrylic adhesive composition
TW201710423A (en) Composition and binder composition

Legal Events

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

Ref document number: 14815120

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14815120

Country of ref document: EP

Kind code of ref document: A1