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Leather and soiling: an exploration of current anti-soiling technologies Dr. Dietrich Tegtmeyer Vice President Product Development and Application Business.

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Presentation on theme: "Leather and soiling: an exploration of current anti-soiling technologies Dr. Dietrich Tegtmeyer Vice President Product Development and Application Business."— Presentation transcript:

1 Leather and soiling: an exploration of current anti-soiling technologies Dr. Dietrich Tegtmeyer Vice President Product Development and Application Business Unit Leather

2 SLTC; September 26th, Antisoiling Systems For A Change In Leather - leather is a classic yet highly fashionable article - leather undergoes a continuous development with regards to its longevity - due to the consumers requirements the color shades of leather goods have changed over the past - color shades have become lighter

3 SLTC; September 26th, Antisoiling Systems The Challenge - bright colors are by nature more sensitive to soiling and staining - enhanced anti-soiling / anti-staining and cleaning behavior are of need - performance and esthetics of leather must be maintained - leather must remain leather with all its desirable properties

4 SLTC; September 26th, Antisoiling Systems Basics Definitions and Theory Differentiation of Performance Characteristics Testing of Antisoiling Characteristics Chemistry of the New Antisoiling Technology Test Results Summary / Conclusions Todays Agenda

5 SLTC; September 26th, Antisoiling Systems Nano foam Nano particles 1 Nanometer = 0, meter = 1 * 10 EXP-9 meter 1 nm :1 mm football: earth Picture: GNU Free Documentation License Nano colloids Nano tubes Basics – Definition of Nano Technology

6 SLTC; September 26th, Antisoiling Systems bis 160 ° Pictures: GNU Free Documentation License Basics – Definition of Lotus Effekt

7 SLTC; September 26th, Antisoiling Systems Basics – Lotus Effect means a self cleaning capability of the surface Pictures: GNU Free Documentation License

8 SLTC; September 26th, Antisoiling Systems Aesthetical properties Touch Feel Smell Many requirements for a finishing chemistry Fasteness properties Hydrolysis Lightfastness Color Strength Physical properties Abrasion Adhesion Flex Antisqueek Process properties Recoatability Flow out Drying Staking

9 SLTC; September 26th, Antisoiling Systems print binder elasticity lowhigh flex General problem: if you optimize one of the properties, you are sacrifying others A lot of criteria are behaving complementary Challenge for chemistry: we have to look for the best compromise or for the application: we have to formulate around weaknesses

10 SLTC; September 26th, Antisoiling Systems Aesthetical properties ANTISOILING Touch Feel Smell Anti-soiling is one additional category, also complementary to important other requirements ? Fasteness properties Hydrolysis Lightfastness Color Strength Physical properties Abrasion Adhesion Flex Antisqueak Process properties Recoatability Flow out Drying Staking Anti-soiling Recoatability

11 SLTC; September 26th, Antisoiling Systems matting system binder chemistry degree of X-linking additives e.g. thickener embossing drying conditions Anti-soiling is a very complex requirement and influenced mainly by surface parameters of the leather Surface Morphology physics Substance chemistry Marcro Scale > 1 µm Micro Scale 10 – 1000 nm Hydrophobicity Oleophobicity

12 SLTC; September 26th, Antisoiling Systems Macro Scale: Surface Porosity of a conventional top coat A high amount of holes visible on the surface in a range of 5 µm 5.5 µm

13 SLTC; September 26th, Antisoiling Systems A small amount of holes visible on the surface in a range of 5 µm Macro Scale: Surface Porosity of a conventional top coat with good anti-soiling perforance

14 SLTC; September 26th, Antisoiling Systems Surface Porosity of a top coat of the new PTFE Copolymer Basically zero holes visible on the surface in a range of 5 µm Less penetration of soil can be easier cleaned away, but after soiling it also appears more dirty on the surface!

15 SLTC; September 26th, Antisoiling Systems e.g. little pins on the surface in nano range could lead to a self cleaning effect Micro Scale: Surface structure of a lotus leave Pictures: GNU Free Documentation License

16 SLTC; September 26th, Antisoiling Systems matting system binder chemistry degree of X-linking additives e.g. thickener embossing drying conditions Surface Morphology physics Substance chemistry Marcro Scale > 1 µm Micro Scale 10 – 1000 nm Hydrophobicity Oleophobicity Anti-soiling is a very complex requirement and influenced mainly by surface parameters of the leather

17 SLTC; September 26th, Antisoiling Systems A good antisoiling performance is not the result of one single additive - but one wrong single additive could have a very negative impact for some tests acrylic chemistry is better suited than PU chemistry low concentration of emulsifier only special silicons are required special matting agents, which generate a small surface and have a low porosity high X-linking, not only for the permanence, even for the antisoiling effect special additives can improve the anti-soiling performance The right formulation is one of the important basics

18 SLTC; September 26th, Antisoiling Systems Adhesion of dirt is determined by the surface chemistry Hydrophobicity Oleophobicity Silicon Area PTFE Area Parafin Area the best anti-soiling characteristic should be in the right upper square Additives and binder chemistry do influence the surface properties

19 SLTC; September 26th, Antisoiling Systems Basics Definitions and Theory Differentiation of Performance Characteristics Testing of Antisoiling Characteristics Chemistry of the New Antisoiling Technology Test Results Summary / Conclusions Todays Agenda

20 SLTC; September 26th, Antisoiling Systems Requirements Anti-Staining: - mainly required by the furniture industry Anti-Soiling: - mainly required by the automotive industry Cleanabilty: - required by both furniture and automotive industry

21 SLTC; September 26th, Antisoiling Systems 1. Dirt Dirt The contamination of leather must be differentiated by different pollutants: Staining: - accidental and occasional contamination of leather - wine, coffee, lipstick, ball pen etc. before soiling after soiling Soiling Soiling: - constant exposure of leather to dirt throughout daily use - ambient dust, dyestuffs from garment, carbons, oils etc. Staining

22 SLTC; September 26th, Antisoiling Systems What is soiling / cleanability about ? We differentiate between … Cleanability: - The behavior of leather surfaces to cleaning after a contamination has occured - Can the contaminant(s) be removed ? - How easily can the contaminant(s) be removed ? - How much residue remains on the leather surface ? Durability of anti-soiling finishes: - Gives an indication about the longevity of anti-soiling finishes - How many times can a leather be soiled and cleaned maintaining it anti-soiling / cleanability performance ? 2. Cleaning Cleaning

23 SLTC; September 26th, Antisoiling Systems 3. Testing Testing Different kinds of dirt are applied and cleaned by different test methods. Staining: - is tested by applying the contaminants onto the leather directly - subsequently the dirt is wiped off with common household cleaners - cleaning efficacy is evaluated and rated after stainingafter cleaning

24 SLTC; September 26th, Antisoiling Systems Testing Soiling: - standardized fabrics, contaminated with different pollutants are rubbed over the leather by means of the Martindale abrasion tester - after cycles the degree of color change on the leather is measured - subsequently the dirt is wiped off by means of common leather cleaners and the color change is measured again Conventional Finish after soiling after cleaning Attention: different testing procedures do result in different data !

25 SLTC; September 26th, Antisoiling Systems How is soiling tested ? Anti-Soiling 1 ( VDA Test ): - Contaminants are applied on the leather by standardized soiling clothes*. *EMPA 104: polyester/cotton, soiled with carbon black / olive oil *EMPA 128: cotton jeans with indigo/sulfur black, soiled with carbon black / olive oil EMPA 104 EMPA 128 without X-Shield top with X-Shield top before after cleaning before after cleaning EMPA 104 with X-Shield top without X-Shield top before after cleaning before after cleaning EMPA 128 Different contamination

26 SLTC; September 26th, Antisoiling Systems How is soiling tested ? Anti-Soiling 1 ( VDA Test ): - Testing is done by Martindale abrasion tester: cycles, weight 12Kpa, large Lissajous figure with: - Pilling holder* ( Ø 140 mm ) or - Abrasion holder* (Ø 38 mm ) ( *depending on specification ) - Degree of soiling before cleaning: Requirement: 3 ( grey scale ) - Degree of soiling after cleaning: Requirement: 4-5 ( grey scale ) Abrasion holder, Ø 38 mm without X-Shield top with X-Shield top before after cleaning before after cleaning Pilling holder, Ø 140 mm without X-Shield top with X-Shield top before after cleaning before after cleaning Different holders/conditions

27 SLTC; September 26th, Antisoiling Systems How is soiling tested ? Anti-Soiling 2 ( Dye Ingress Test ): - Contaminants are applied on the leather by a standardized soiling cloth*. *standard JLR denim fabric with indigo dye, soaked in alkaline sweat solution ( BS1006 E04 ) soiling cloth cleaning cloth Different testing fabrics/conditions

28 SLTC; September 26th, Antisoiling Systems How is soiling tested ? Anti-Soiling 2 ( Dye Ingress Test ): - Testing is done by Martindale abrasion tester: cycles, weight 12Kpa, large Lissajous figure - Abrasion holder ( small specimen holder, 38 mm ) - Degree of soiling before cleaning: Requirement: 4 ( grey scale ) - Degree of soiling after cleaning ( cycles as described above; cleaning cloth soaked in cleaner; e.g. Leather Master car interior leather cleaner: Requirement: 4-5 ( grey scale ) Standard PU Top after cleaning LXS Acrylic Top after cleaning Different testing fabrics/conditions

29 SLTC; September 26th, Antisoiling Systems Basics Definitions and Theory Differentiation of Performance Characteristics Testing of Antisoiling Characteristics Chemistry of the New Antisoiling Technology Test Results Summary / Conclusions Todays Agenda

30 SLTC; September 26th, Antisoiling Systems Individualized Systems - a wide variety of potential contaminants along with an even bigger number of different leather properties require different anti- soiling systems - the goal is to achieve the best possible spectrum of efficacy - TFE ( tetrafluoroethene ) based products have proven to be the best suitable substances for those applications

31 SLTC; September 26th, Antisoiling Systems Polytetrafluorethene ( PTFE ), The Solution PTFE - provides hydrophobic and oleophobic effects at the same time - thermo stable from -200°C to +260° C - chemically inert and resistant against UV radiation - provides low friction and excellent release properties - has extremely low surface energy

32 SLTC; September 26th, Antisoiling Systems TFE Containing Copolymers, Different Options 1. Comb Polymer Advantages: - excellent dirt repellency - excellent initial cleanability TFE containing side chains TFE protection top 2. Linear Polymer Advantages: - excellent dirt repellency - excellent cleanability and durability TFE groups are built into the monomer TFE copolymer binder TFE groups can be incorporated in two different ways

33 SLTC; September 26th, Antisoiling Systems Comb Polymer Structure AQUADERM ® X-Shield L facts: - used as an additive in special top coats - cross-linking of pure product not possible ( limited durability ) - outstanding dirt repellency - outstanding initial cleanability AQUADERM ® X-Shield L Important note: - PFOS (perfluoroctylsulfonic acid) - PFOA (perfluoroctanoic acid) Analysis of leather finished with AQUADERM ® X-Shield L have proven that neither PFOS nor PFOA are detectable.

34 SLTC; September 26th, Antisoiling Systems

35 SLTC; September 26th, Antisoiling Systems With And Without.... Conventional Finish AQUADERM ® X-Shield L Finish after soiling after cleaning

36 SLTC; September 26th, Antisoiling Systems Linear Polymer Structure - TFE copolymers + different functional groups offer a versatile application field to the leather industry Protection coats which consist of AQUADERM ® X-Shield G / M2 - can be pigmented - can be cross-linked with isocyanate - are film forming - allow to adjust different gloss levels - can be fine tuned by the addition of feel agents - provide superior and long lasting abrasion resistance AQUADERM ® X-Shield G / M2

37 SLTC; September 26th, Antisoiling Systems Linear Polymer Structure R 1 | CH- a CF 2 - 2c CH 2 - d 2 - e | - b | XY Z COO - HN + R 3 || R 2 | COO - HN + R 3 | filmformation / transparency antisoiling / cleanability cross-linking / adhesion pigment dispersibility dispersion stability - functional groups: approx. 50 % in total - built-in PTFE segments:approx. 50 % in total

38 SLTC; September 26th, Antisoiling Systems Different To Conventional Fluorine Systems - the X-Shield system is based on a new concept providing permanent protection - the integrated PTFE segments in a polymer backbone are stable against hydrolytic attack ( bound by stable C-C bonds ) - additional segments provide film formation and reactivity - long lasting protection along with environmental soundness R Leather Surface PTFE segment non fluorinated segment TFE-copolymer R NCO OCN cross-linking reaction + R R R R

39 SLTC; September 26th, Antisoiling Systems Cleanability performance as a function of cycles Only one cycle is currently part of automotive specs! Long term cleanability is a new challenge before cleaning after cleaning complementary Antisoiling system conventional PTFE binder cleaning cycle poor excellent

40 SLTC; September 26th, Antisoiling Systems Consistancy of Cleanability performance is an issue Only one cycle is currently part of automotive specs! Long term cleanability is a new challenge cleaning cycle before cleaning after cleaning Antisoiling system conventional PTFE binder poor excellent

41 SLTC; September 26th, Antisoiling Systems cleaning cycle Cleanability performance suffers after pre-treatment A tough pre-treatment influences the anti-soiling performance before cleaning after cleaning Pre-treatment cycles Martindale w/clean cloth 48 h Hydrolysis Antisoiling system Typ A Typ B poor excellent

42 SLTC; September 26th, Antisoiling Systems Special protection top doesnt show soiling at all in all EMPA tests. It is however not a long lasting effect 1 cleaning cycle before cleaning after cleaning Comparison of soiling performance of X-Shield G and L Anti-soiling system conventional PTFE binder PTFE protection top poor excellent

43 SLTC; September 26th, Antisoiling Systems final antisoiling performance depends on article characteristics The Finishing System is playing an important role Gloss level Recoatability Anti squeek Flex Performance Impact on Antisoiling perfomance dull…….medium……….glossy high…….…..medium……...poor excellent…… regular …....… poor excellent..…..good …...… medium decreasing improving Adjustments of certain parameters / physical properties have an impact on antisoiling performance

44 SLTC; September 26th, Antisoiling Systems Basics Definitions and Theory Differentiation of Performance Characteristics Testing of Antisoiling Characteristics Chemistry of the New Antisoiling Technology Test Results Summary / Conclusions Todays Agenda

45 SLTC; September 26th, Antisoiling Systems Two main conclusions 1.) There is no universal system which fullfills overall best performance in terms of Antistaining Antisoiling Cleanability You have to chose the best system for you specific application requirements 2.) You have to minimize the negative impacts of other properties such as dulling, anti squeek, etc.

46 SLTC; September 26th, Antisoiling Systems Best systems for Antisoiling In dependence of the leather goods manufacturers requirements the X-Shield system allows the individual customization of all kinds of leather articles. AQUADERM ® X-Shield L -for optimized anti-soiling and initial cleanability performance in EMPA test HYDRHOLAC AD1 and CL1 -for optimized anti-soiling in Dye Ingress test X-Shield Protected Conventional Finish

47 SLTC; September 26th, Antisoiling Systems AQUADERM ® X-Shield G, ( gloss component ) in combination with AQUADERM ® X-Shield M2, ( matting component ) - for efficient and long lasting anti- staining protection and long term cleanability Conventional Finish before cleaning after cleaning X-Shield Protected before cleaning after cleaning Best systems for Antistaining and Cleanability

48 SLTC; September 26th, Antisoiling Systems Individual systems for individual specifications ProductStainingAnti-Soiling VDA Anti-Soiling Dye Ingress AQUADERM X-Shield Gxx AQUADERM X-Shield M 2 EXP 2002x AQUADERM X-Shield L EXP 2001x HYDRHOLAC AD-1xx AQUADERM Matt HPM-Nx HYDRHOLAC CL-1xx HYDRHOLAC AQSx AQUADERM Additive GFxxx AQUADERM Additive SFxxx ROSILK 2229 FMxx Different systems for different requirements

49 SLTC; September 26th, Antisoiling Systems Summary The AQUADERM ® X-Shield range: - functional products providing additional performance and value to leather industry - unique chemistry for leather - strong effect - significant extra value of the leather article A special labeling is offered to the industry

50 SLTC; September 26th, Antisoiling Systems Thank you for your attention

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