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Technology Trends in Automotive Surface Coatings
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Applied Polymer Research Institute
Technology Trends in Automotive Surface Coatings
Jong Myung ParkBuhmwoo Institute of Tech
November 15, 2006
Applied Polymer Research Institute
CONTENTS
Pretreatment System
Electro-Coat
Pre-sealed System
Pre-primed System
UV-Curing System
Conclusion
Introduction
Basics of Organic Coating System
Applied Polymer Research Institute
환경친화성경량화 안정성 내구성가공성
자동차 강판요구성능
적용 기술
•DP
(Dual Phase)
•TRIP
(Transformation Induced Plasticity)
경량화 및 강도 ,
연신율 우수
고속 충돌성 우수한 고강도 강판
•BH STEEL
Bake hardening steel 약자로 , 차체 성형시 강도가 낮아 가공성 우수하고 , 성형 후에는 자동차 도장공정을 거치면서 받는 열에 의하여 강도가 증가되어 최종 자동차 완성된 이후 높은 강도 구현 가능 .
고내식성
표면처리 강판
•Presealed •Preprimed
•Pre-finished
•Pb,Cr-free
표면처리 강판
• 고강도강 사용으로 차체무게 감소 – 연비 감소로 인한 환경오염 배출물질 감소
Introduction
The Technology of Properties for Automotives
Applied Polymer Research Institute
Purpose of Coatings for Automotives
Protect from
미관 상품성 향상
방 청
방 음
입체감
평활성
광택감
색
채
SUN LIGHT(UV, IR)
Water, Oxygen
Sand, Dust
Gum, Soot
Sea breeze
Exhaust gas
Improve
Introduction
Applied Polymer Research Institute
Coating Process of Car Body
Introduction
Applied Polymer Research Institute
Higher QualityHigher Quality
1.Appearance and Durability2.Color and Corrosion resistance
1. Cut-down Production Process2. Save Labor Usage
Lower Cost
1. Lower Paint Usage2. Reduce VOC3. Reduce Waste Water
EnvironmentalCompliance
1. Direct Coating on Steel Sheet2. Co-work Automotive & Steel Company
ShorterDevelopment
Times
Global Automotive Paint Driving Force
Introduction
Applied Polymer Research Institute코팅 시스템 개론
일반적 코팅 구성 성분
Resin
Adhesion & Film formation
Key Ingredient for performance
Solvent
Rheology control
Solvation & Dilution
Drying behavior
Additive
Defoaming
Rheology control
Surface wetting/levelling
Pigment
Surface protection
Special function
Decoration/Color
Protection
Functionality
Decoration
(Automotive, Heavy-duty,
PCM, Industrial)
UV protection
Applied Polymer Research Institute코팅 시스템 개론
코팅용 수지
Applications
- Automotive Refinish
- Architectural (Emulsions)
- Vacuum Metallizing, NC
Binder = Film Former = Polymer = Resin
* Thermo-plastic Resin ( 열가소성 )
- High Mw Polymer 에 의하여 생성
- No Functionality for Crosslinking
- Low-solid System
- Solvent Evaporation 에 의하여 도막 형성
- Solvent 및 Heating 에 의하여 재용해 특성
- Latex – Aqueous Acrylic Dispersion
- High VOC System
소재 표면에 접착 및 부착되어 Film Formation 및 형성된 필름의 물성을 좌우하는 가장 중요한 코팅 성분
Characteristics
- Quick Drying
- No Chemical Change
- Re-dissolved
Applications
- Automotive OEM
- Can Coatings
- Coil Coatings
- Appliance Finishes
- 2K PU Coatings
* Thermo-setting Resin ( 열경화성 )
- Low Mw Polymer
- Crosslinking System
- Crosslinker 와 반응할 Functional Group 필요
- Solvent 및 Heating 에 의하여 재용해 어려움
- Acrylics 및 Polyester, Alkyds, Epoxies 등
- Lower VOC System
Characteristics
- Heat System
- Chemical Change
- Not Easily Re-dissolved
Applied Polymer Research Institute코팅 시스템 개론
Resin Crosslinking
수지의 Reactive Functional Groups 과 Crosslinker 간의 화학적 반응에 의하여 생성되는 3 차원 Polymer Network
* Crosslinking Technology 장점
- Low Mw Resin --- Easily Soluble
- High Solids Level 가능
- 범용적인 다양한 수지 및 경화제 군
- Heat 조건에서 용해되지 않음
- 우수한 Solvent Resistance
- Low Mw 로 인하여 Compatibility 양호
* Crosslink 위한 화학 반응
- Oxidation
- Melamine Crosslink
- Isocyanate Crosslink
- Epoxy Crosslink
Resin Functionality Crosslinkers
Hydroxyl Group (-OH)
Carboxyl Group (-COOH)
Epoxies
Unsaturated Fatty Acid
Amino Resins / Poly-isocyanate
Amino Resins / Epoxies
Polyamines / Poly-carboxylic Acid
Oxygen
Applied Polymer Research Institute코팅 시스템 개론
코팅용 수지 구분
Thermosetting Resin
Air-drying
2-K Reactive
Baking Type
Stand Oil/Bodied Oil
Varnish (Oleoresinous Varnish)
Ambient Dried Alkyd Resin
Polyurethane Resin
Epoxy Resin
Alkyd Resin
Polyester Resin
Thermo-setting Acrylic Resin
Melamine Resin
Phenol Resin
Blocked Isocyanate
Urea Resin
Thermoplastic Resin
Cellulose (NC & CAB)
Chlorinated Rubber
Thermo-plastic Acrylic Resin
Vinyl Resin
Applied Polymer Research Institute
구성 성분 Acrylic Monomer
Initiator
Organic Solvents
Emulsifier
Properties Versatile / Durable
Good Color
Gloss Retention
Good Resistance
- UV
- Hydrolysis
- Oxidation
Characteristics Solvent Composition
Molecular Weight
Tg
Solubility
Uses Automotives
Heavy Industries
Industrials
Architectures
Special Applications
Acrylic Resin
코팅 시스템 개론
Applied Polymer Research Institute
Acrylic Resin Crosslinking Reaction
코팅 시스템 개론
O
OHO
OH
OH
O N
CH2OR
(ROCH2)2N
O NR
N O
O O
H H
OCN R NCO
OH
Epoxy
I socyanate
Amino-Formaldehyde
Applied Polymer Research Institute
Amino Resin
코팅 시스템 개론
Urea / Melamine
Formaldehyde
Alcoholic Solvent
Brittleness
High Speed Cure
Self-condensation
Mineral Spirits Tolerance
Alkoxy Type & Degrees
Solubility & Compatibility
Stability
Cure Rate
Acrylic Polyol
Polyester Polyol
Alkyd
Special Applications
Raw Material Characteristics
Properties Uses (for Crosslink)
Applied Polymer Research Institute
NH2
O
H2N C
OH
NH
N
N
N
NH2NH2
NH2
C
O
CH H HOCH2OH HCHO HOCH2O(CH2O)nH
H2N
(Urea) (Amine) (Imide)
(Melamine)
, + n
(Formaldehyde) (Para-Formaldehyde)
NH2
O
CH2N
O
CH H
O
CH2N
H
NCH2OH
NH HOCH2N NCH2N OH2
NCH2OH HOR NCH2OR OH2
+
(Formaldehyde) (Methylol Urea)
+ +
(Urea)
(Imino±â) (Methylol±â) (Methylene Bridge)
+ +(Methylol±â) (Alcohol) (Alkoxy±â)
Amino Resin 반응 메커니즘
Applied Polymer Research Institute
Polyester Resin
코팅 시스템 개론
Acid
Alcohol
Solvents
Flexibility
Good Adhesion
Good Chemical Resistance
Solvent Composition
Molecular Weight
Industrials
Pre-coated Metal
Heavy Industries
High Crosslinking Density Automotives
Raw Material
Properties
Characteristics
Uses
Good Hardness
Applied Polymer Research Institute
Polyester Resin 반응 메커니즘
코팅 시스템 개론
OHH2C
H2C OHn + HOOC COOHn
ethylene glycol
terephthalic acid
OH2C
H2C O C
O
C O
O n
+ 2nH2O
polyethylene terephthalate
ISOCYANATE CROSSLINKS WITH HYDROXYL RESIN
N
O
CN
HR
O
ECAP ISOCYANATE
R N C O
-
CAPROLACTAM
N
HO
+ R' OH R N
C
H
OO
R'POLYESTER RESIN
URETHANE
CAPPOLY.CW210/96
OCN CH2 N N CH2 NCO
O
O
OR
SELF BLOCKED IPDI
CROSSLINKERS FOR CARBOXYL RESINS TGIC , PRIMID & EPOXY
HO
N C
O
(CH2)n C
O
N
HO
OH
OH
TGICPRIM.cw2
10/96
CH2 CH
O
CH2
OO
O
N
N
N
CH2
O
CHCH2
CH2
O
CHCH2
TGIC Primid XL552 (EMS)(CIBA)
BASED ON BISPHENOL A AND EPICHLOROHYDRIN
n
O
CH2 CH CH2 O C
CH3
CH3
O CH2 CH CH2
OH
O C
CH3
CH3
O CH2 CH
O
CH2
EPOXY
Applied Polymer Research Institute
CH2 CH
O
CH2
OO
O
N
N
N
CH2
O
CHCH2
CH2
O
CHCH2
TGIC
+
R C
O
OH
H2C CH CH2
OO
O
N
N
N
CH2CHCH2
CH2CHCH2
OH
O
C O
R
OHO
CO
R
OH
O
CO
R
PE&TGIC.CW2 10/96
3
TGIC CROSSLINKS WITH CARBOXYL POLYESTER
CARBOXYL POLYESTER
+CH2 CH
O
CH2 O R
HYBRID
PE&EPOXY.CW210/96
2
COH
O
OHOC
OOC
R
CO O
CO O CH2 CH
OH
CH2 O R
R
ROCH2
OH
CHCH2OOC
EPOXY CROSSLINKS WITH A CARBOXYL POLYESTER
CARBOXYL POLYESTER
EPOXY
Polyester Resin 반응 메커니즘
코팅 시스템 개론
Applied Polymer Research Institute
Epoxy Resin
코팅 시스템 개론
Bis-phenol A
Epichlorohydrine
Solvents
Good Reactivity
Good Chemical Resistance
No Side Products
Solvent Composition
Molecular Weight
Industrials
Heavy Industries
Automotives
UV Sensitivity Floor Coatings
Electronics
Raw Material
Properties
Characteristics
Uses
Good Mechanical Properties
Applied Polymer Research Institute
OH C OH
CH3
CH3
+O
H2C CH CH2 Cl
BPAECH(EXCESS)
NaOH
O- Na+
Sodium Phenoxide
H2C CHO
CH2 Cl+ O CH2 CH
OH
CH2 Cl
O CH2 CH
OH
CH2 Cl
NaOH
O CH2 CH CH2
O+ NaCl + H2O
OH C OH
CH3
CH3
BPA
+ NaOH + H2O
O-
CH2 CHO
CH2 O C
CH3
CH3
O CH2 CH CH2
OH
O C O
CH3
CH3
CH2 CH CH2
O
n
Epoxy Resin 반응 메커니즘
코팅 시스템 개론
OH
È°¼º¼ö¼ÒÈ ÇÕ¹°
BºÎ °¡ ¹ÝÀÀ
O CH
CH2
CH2
OH
Cl
1,3-Chlorohydrin
H2C
O
CH CH2 Cl
ECH
a-ºÎ °¡ ¹ÝÀÀ
O CH2 CH
OH
CH2
Cl1,2-Chlorohydrin
O CH2 CH CH2
O
NaOH
Æóȯ
H2C
O
CH CH2 Cl
ºÎ °¡ , Æóȯ
O CH2 CH CH2
ClO
CH2 CH CH2
O
O CH2 CH CH2
OHOH
°¡ ¼öºÐÇØ
H2O
1,2- Glycol
Glycidylether + NaOH + H2O
°í ºÐÀÚÈ OH
O CH2 CH
OH
CH2 O
ÁÖ¹ÝÀÀ
ºÎ ¹ÝÀÀ
Applied Polymer Research Institute
Urethane Resin
코팅 시스템 개론
Isocyanates
Glycols
Solvents
Good Adhesion
Good Mechanical Properties
High Gloss
Isocyanate Type
Cure Rate
Sealants
Architectures
Industrials
Hardener for Acrylics
Hardener for Polyesters
Raw Material
Properties
Characteristics
Uses
Good Electro-isolation
Easily Gellation
Yellowing
Applied Polymer Research Institute
CH3
NCO
NH OCO -------OCC NH
NCO
CH3
Urethane Resin 반응 메커니즘
A) (Prepolymer) + H2O
B)CH3
NH2
NH
OCO --------OCC NH
CH3
NH2
( 중간체 Amine 구조 ) + CO2
↑
상온 경화형
C O
NH
CH3
CH3
NH
NH
NH
OCO------------
OCO------------
OCO
OCO
NH
NH
CH3
NH
C
O
CH3
NH
A + B
2 액 경화형
A)
B)
CH3
NCO
NH OCO -------------OCC NH
NCO
CH3 (Prepolymer)
HO ----------------- OH (Polyol)
----- OCONH NH OCO -------
CH3
n
A + B
코팅 시스템 개론
Applied Polymer Research Institute
Pigments 구분 및 역할
코팅 시스템 개론
도막형성 물질과 혼합되어 , 색상과 은폐 , 투명성 제공 및 기후와 부식에 대한 저항성 , 도막 강화 기능 등 부여
Pigments
Titanium Dioxide
Prime Pigment
Extender Pigment
High Refractive Index (Scatter Light)
High Cost
Organic & Inorganic (Oxides)
Calcium Carbonate, Talc, Clays
Barium Sulphate, Silicas
* Reactive Pigments
(Rust Protection – Passivation)
- Borates
- Chromates
- Leads
- Molybdates
- Phosphates
- Silicates
* Barrier Pigments
- Talc
- Aluminum
- Mica
- Silver Paste
Organic pigment
Organic pigment
Property Inorganic pigment
Inorganic pigment
Polarity non polar polar
Surface area large small
Particle size small large
Color
Shade
Transparency
Hiding Power
Applied Polymer Research Institute
Pigment Dispersion
코팅 시스템 개론
Dispersion
Flocculation
Primary Particle
(Ideal Dispersion)
Agglomerate
Flocculate ( 고체 / 기체 )
Flocculated ( 고체 / 액체 ) Deflocculated ( 고체 / 액체 )
Wetting Dispersing Stabilization
Coating System Stabilization Mechanism
Solvent-Based Steric Hindrance / Charge
Water-Reducible Charge / Steric Hindrance
Emulsion Charge Stabilization
Repulsion Attraction
Applied Polymer Research Institute
Solvents 역할
코팅 시스템 개론
수지 및 기타 원료의 용해 , 원활한 작업 위한 점도 조절 그리고 코팅 안정성 및 흐름성 조절 용도로 사용
Evaporation Rate
Solvent Diffusion
Solvent Activity
Characteristics
Viscosity
Diffusion Ratio
Density
Water Solubility
Electrical Resistance
Total Cost in Use
Right Solvency for the Application
Evaporation Rate
Issues
HAPs, VOC Regulation Compliance
Odor & Toxicity
Solvents
Active Solvents
Latent Solvents
Diluent Solvents
Dissolve Resin
True Solvent for NC
Lower Viscosity
High Cost
Assist the Active Solvents
Reduces Viscosity
Poor or Non-solvent Alone
Intermediate Cost
Diluents the System
Non-solvent
Low Cost
Ketones / Esters
Glycol Ethers
Glycol Ether Esters
Alcohols
Water
Aromatic Hydrocarbons
Aliphatic Hydrocarbons
Applied Polymer Research Institute
Dissolve Film Formers
Paint Removers
Cleaning Metals
Cleaning Fluids
Coalescing Aids
Uses
Solvent Type Aromatic HC Alcohol Ester KetoneP-series
(Dow)E-series
(Dow)
Typical Solvent Xylene IPA or ButanolN-BuAc or
n-BuPrMEK or MIBK PM or PMA EE or EEA
Resin Solubility
(Acrylics)Good Poor Good Excellent Fair Fair
Resin Solubility
(Epoxies)Good-Fair Poor Good Excellent Fair Good-Fair
Evap. Rate Mid Fast Fast-Mid Fast Mid-Slow Mid-Slow
Odor Poor Good-Fair Fair Poor Good-Fair Good-Fair
Toxicity Poor Good Good Fair Excellent Poor
Regulatory
CompliancePoor Good Excellent Fair Excellent Poor
Solvents 비교
코팅 시스템 개론
Applied Polymer Research Institute
코팅용 Solvents
코팅 시스템 개론
Solvent-based Water-based
WaterborneWater reducibleHigh solidsConventional coatings
ResinResin
Active solventActive solvent
SolventSolvent(Dilutant)(Dilutant)
ResinResin
CouplerCoupler
WaterWater
ResinResin
Active solventActive solvent
SolventSolvent
ResinResin
WaterWater
CoalescentCoalescent
Coatings
Organic Loving Water Loving
Alkyl Portion Glycol Head
CH3CH2CH2CH2 O CH2CHOH
CH3
CH3
CH3O CH2CHOCH2CHOH
CH3
Alkyl PortionGlycol Head
DOWANOL PnB
DOWANOL DPM
Solvent Partitioning
Applied Polymer Research Institute
Additives for Coatings
코팅 시스템 개론
Additives
Dispersants
Wetting Agent
Defoamer
Control to Pigment Particle Sizes
Pigment Stabilization
(Electrostatic & Steric Stabilization)
Thickener
UV Stabilizer
Control to Surface Tension
(Silicone & Fluoro Chemistry)
Control to Foam
(Waterborne System)
Control to Viscosity
(ASE, HASE, HEUR, Bentone, Cellulose)
Protection to UV Ray
(Hydroxyphenyl triazine, Benzotriazole )
Applied Polymer Research Institute
Lower molecular Higher molecular
Wetting Agents 특성
코팅 시스템 개론
Wetting Agents
Anionic Surfactant
Cationic Surfactant
Amphoteric Surfactant
Hydrophobic Group with Hydrocarbon
12-18 Alkyl Group with –COOH, -SO3H, -OSO3H
-COONa, -SO3Na → Salt Shape
Non-ionic Surfactant
Hydrophilic Group with Cation
-CH2N+CH3Cl-
Surfactant with Anionic and Cationic both
R1-(NH-CH2CH2)2-NH+-CH2-COO-
Non-ionic System
Polyethylene Oxide Compound
––
––––
–– –
Ionic Type Non-ionic Type
With Additive Without Additive
Applied Polymer Research Institute
Surface Tensions
80
70
60
50
40
30
20Xylol
Water
White spirit
Melamine resins
Alkyd resins
Acrylate
Resins
Phosphatizedsteel
Untreated steel
SMC-Polyester
mN
/m
Solvents Resins Substrates
aqueous
Surface Tension
코팅 시스템 개론
Levelling additives
Applied Polymer Research Institute
Defoaming
코팅 시스템 개론
Hydrophobicparticles
Foam lamella
Polydimethylsiloxanes
compatible incompatible
2 - 30 45 - 230 1800 - 2900380 - 1500
DefoamingFlow Slip Hammertone
x
(CH3)3 Si O Si O Si (CH3)3
CH3
CH3 x
No Defoamer with Defoamer
Applied Polymer Research Institute
Thickener (Rheology)
코팅 시스템 개론
newtonian: = const.
pseudoplastic: = f(D)(shear thinning)
visc
osi
ty
shear rate D
Viscosity Curve
shear rate D
visc
osi
ty
= f (time t)
Thixotropy
Flow cup 4 mm ICI cone/plate
Brookfield
storage
leveling
settling sagging
transportation production
stirring application
Rotational viscometer
0,1
viscosity (Pa·s)
0.01 0.1 1 10 100 1000 100000.001
shear rate D (1/s)
100
10
1
Viscosity Profile
Applied Polymer Research Institute
UV Stabilizer
코팅 시스템 개론