Light stabilizers and antioxidantsLight stabilizers and antioxidants

Principles of Light stabilizersPrinciples of Light stabilizers

Degradation of polymersDegradation of polymers

•• OxygenOxygen•• Peroxides:alcohols,ketones,aldehydesPeroxides:alcohols,ketones,aldehydes,,

acids, acids, peracidsperacids•• Energy: mechanical Energy: mechanical stress,heat,UVstress,heat,UV

lightlight•• Air Air pollution:NOx,SOxpollution:NOx,SOx……•• Heavy Heavy metals:Metalsmetals:Metals//--ionsions

Consequence of polymer degradation

Loss of mechanical properties Color changeChange in claritySurface chalkingLoss of glossShortened service life Crack

Intensity distribution of sunshineIntensity distribution of sunshine

•• 0.70.7--280nm280nm---------- 0 %0 %•• 280280--400nm400nm--------UV light UV light 6%6%•• 400400--750nm750nm--------Visible light Visible light 52%52%•• 750750--3000nm3000nm------Infred lightInfred light 42%42%

Light stabilizersLight stabilizers

•• UV absorbersUV absorbersprovide a screening effect by competitively provide a screening effect by competitively absorbing UV light absorbing UV light

•• QuenchersQuenchersdeactivate the excited states of the deactivate the excited states of the chromophoreschromophores

•• Free radical scavengersFree radical scavengersinterrupt the autointerrupt the auto--oxidation process by oxidation process by scavenging free radicalsscavenging free radicals

UV absorberUV absorber

•• What is UV ? UVC : below 280 nm What is UV ? UVC : below 280 nm (mainly screened by Ozone layer) (mainly screened by Ozone layer) UVB:280UVB:280--320nm, UVA: 320320nm, UVA: 320--400nm 400nm

•• BenzotriazoleBenzotriazole•• BenzophenoneBenzophenone•• AcrylateAcrylate•• ReactableReactable•• OthersOthers

••KLYKLY1 KLY=1 Kcal/cm1 KLY=1 Kcal/cm2 . 2 . yearyearFlorida approx. 140KLY /yearFlorida approx. 140KLY /yearArizona approx. 190KLY /yearArizona approx. 190KLY /yearTaiwan approx. 120Taiwan approx. 120--140KLY /year140KLY /year

•• AFUAFU

Rating of lightnessRating of lightness

• AATCC & ISO method :Gray scale for colorchange & stainΔE*,L*,a*,b*

UV AbsorberUV Absorber

•• BenzophenoneBenzophenoneChisorb BPChisorb BP--3 ,BP3 ,BP--1212

CHISORB BP-3

0

0.5

1

250 275 300 325 350 375 400 425 450

Wavelength (nm)

Abso

rban

ce

*1.2 mg of BP-3 in 100 ml of Methanol

O OH

R

O OH

R

ChisorbChisorb

BenzophenoneBenzophenone•• Chinox BPChinox BP--11•• Chisorb BPChisorb BP--33•• Chisorb BPChisorb BP--44•• Chisorb BPChisorb BP--1212

OOH

OR

•• BenzotriazolesBenzotriazolesChisorb P, 234,325,326,327,328,5103,5228S,5411,5431,5687

N

NN

OH

R2

R1

R3

CHISORB 328

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

250 300 350 400 450

Wavelength (nm)

Abso

rban

ce

ChisorbChisorb

BenzotriazoleBenzotriazole 11•• Chisorb PChisorb P•• Chisorb 320Chisorb 320•• Chisorb 325Chisorb 325•• Chisorb 326Chisorb 326•• Chisorb 327Chisorb 327•• Chisorb 328Chisorb 328

N

NN

OH

R

R'

ChisorbChisorb

BenzotriazoleBenzotriazole 22•• Chisorb 234Chisorb 234•• Chisorb 5411Chisorb 5411•• Chisorb 5431Chisorb 5431

N

NN

OH

R

R'

•• OthersOthers::dialkylaminobenzoicdialkylaminobenzoic esterester

Acrylate,BenzoateAcrylate,Benzoate, , MethoxycinnamateMethoxycinnamate ,,OxanilideOxanilide …………....Chisorb 335,336,971,389,1268,5540Chisorb 335,336,971,389,1268,5540……..

CN

OC2H5O

O

OHO

CN

O-CH2-CH-C4H9

O C2H5

ChisorbChisorb

AcrylateAcrylate•• Chisorb 335Chisorb 335•• Chisorb 336Chisorb 336OthersOthers•• Chisorb 1300,1500 (antiChisorb 1300,1500 (anti--NOX, antiNOX, anti--gas fading )gas fading )•• Chisorb 1268Chisorb 1268•• ChisorChisor SUVSUV•• Chisorb 2260Chisorb 2260

OO

C N

R

Performance of quenchersPerformance of quenchers

•• Environmentally unfriendly, contamination Environmentally unfriendly, contamination of soilof soil

•• Not popularly used nowNot popularly used now•• Slowly phase out from the marketSlowly phase out from the market

HALSHALS

•• HALS general combined with UVA in most HALS general combined with UVA in most application application

N R N-O

N-O + R

N-ON-O

N-O-R + R’OO

N-O-R

ROOR’+ N-O

(O)

Hindered Amine Light StabilizerHindered Amine Light Stabilizer

•• MonomerMonomer

Chisorb 770Chisorb 770

Liquid typeLiquid typeChisorb,292,353Chisorb,292,353

HN O

O

(CH2)8

O

O NH

N

H3C CH3

H3C CH3

H3C C

O

(CH2)8 C

O

O O N CH3

CH3H3C

CH3H3C

ChisorbChisorb

•• Chisorb 770Chisorb 770•• Chisorb 292Chisorb 292•• Chisorb 622Chisorb 622•• Chisorb 944Chisorb 944•• Chisorb 519 Chisorb 519 (anti(anti--pesticide, acid rain )pesticide, acid rain )

Hindered Amine Light StabilizerHindered Amine Light Stabilizer•• OligomerOligomer

Chisorb 622,944,519Chisorb 622,944,519……

•• Chisorb 519Chisorb 519

NOH (CH2)2 O C (CH2)2

O

C

O

OCH3n

N N

NC4H9

N N

N

N

NR NR NHR

C4H9

(CH2)3 C(H2)2 (CH2)3RNH

whereby R=

N

H

N (CH2)6 N

N

H

N

N N

HN CH2

CH3

CH3

CH3

CH3

CH3

n

ChisorbChisorb

ReactableReactable•• Chisorb 5687 ( double bond remained )Chisorb 5687 ( double bond remained )•• Chisorb 5103 ( 2Chisorb 5103 ( 2--OH function )OH function )

ChisorbChisorb

ReactableReactable•• Chisorb 5687Chisorb 5687

N O

O

2010/3/162010/3/16

RReactable UV absorbereactable UV absorber

Chisorb 5103 UV-spectrum (Chisorb 5103)

0

0.2

0.4

0.6

0.8

1

200 250 300 350 400 450 500

Wavelength (nm)

Abs

orba

nce

NN

NOH ROH

ROH

Benefit : - Good dispersion with high molecular weight , could be used as reactive UVA without migration- Used as di-functional polyol in PU , polyester system reacted in back bond , possible for long term application and food contact application

2010/3/162010/3/16

Water borne UV absorberWater borne UV absorberChisorb 5228 S

Benefit : - Water soluble UVA , used for water borne system , and textile application improve light fastness

Chisorb SPF-1 : emulsified UVA

Benefit :

- Water soluble UVA , used for water borne system , and textile application improve light fastness , such like Nylon, silk, wool

NN

NOH R

SO3Na

Weatherability of LDPE film

Specimen:200um LDPE filmExposure:Q-U-V accelerated weathering tester, Lamp UVB-313Cycle Time:4Hrs. UV at 60℃ / 4Hrs. condensation at 50 ℃.Additive: Antioxidant 0.05% Chinox1076

Sample Exposure time to 50% retained elongation

Control 600 hrs

0.2% Chisorb944 2800 hrs

Stabilization Time to chalkingControl 700 hours

0.2% Chisorb944 2100 hours

0.2% Chisorb519 2450 hours

Light stability of PP plaques

Specimen::2 mm thickness injection moulded plaquesFiller:0.2% Ca-stearate

Antioxidants:0.05%Chinox1010+0.05%Chinox168Weather-o-meter:Xenon arc weather-o-meter

Fig. The yellowing effect of QUV exposure on epoxy with different pretreatmentAfter each 200 hrs ExposureFormulation: Epoxy ( anhydride hardener )+ 1%UV Absorber (or without) ,Exposure: QUV 313, Temp: 50o C* Out door test for 2 months has similar performance

Test result Blank TP-10 EPL Benzotriazole UVA

Heat resist F O F X

UV resist X F O X

O: Good, F: Fair, X: Yellowing

New tendency and possible applicationNew tendency and possible application

•• UVA: UVA: Polymerizable UVA,Polymerizable UVA,1.For high UVA concentration coating to protect 1.For high UVA concentration coating to protect

the subject beneath of coating like solar film.the subject beneath of coating like solar film.2. Long term durability , such like automobile 2. Long term durability , such like automobile

paint without migrationpaint without migrationChisorb 5103 for PU, polyester system systemChisorb 5103 for PU, polyester system systemChisorb 5687 for acrylic,rubber systemChisorb 5687 for acrylic,rubber system

Principles of antioxidantsPrinciples of antioxidants

AntioxidantsAntioxidants•• Primary antioxidantsPrimary antioxidants::

Chinox 7,35,S35,1076,1010,1024,1098,1330,3114Chinox 7,35,S35,1076,1010,1024,1098,1330,3114------

OH

CH3 CH3

O*

ROO* ROOH

CH3

O*

CH3

O

*ROO*

O

OORCH3

+

+ +

HO CH 2CH 2CO[ OCH 2]4

C

OH

CH3

OH

CH3

1.2n

+ +

+

•• BHTBHT

CH3

O

*

CH3

O

*

CH

O

CH

O

++

2010/3/162010/3/16

Chinox 35

Liquid version of anti-oxidant , designed for polyol application

OH

O

O

iC8H17

•• Secondary antioxidantSecondary antioxidant::

PhosphitePhosphiteChinox 168,618,626,DP,TPChinox 168,618,626,DP,TP--1010……

•• ThioesterThioesterChinox DLChinox DL

SR2

R1

ROOH OSR2

R1ROH+ +

P(OR)3 ROOH OP(OR)3 ROH+ +

[ O3] P

SCH2CH2

CH2CH2

COOC12H25

COOC12H25

+ +

+ +

•• Metal deactivatorMetal deactivator::Chinox 1024Chinox 1024

HO CH2CH2

O

NHNH OHH2CH2C

O

Stabilization of LDPE

Additives:0.05% Chinox10100.05% Ca-St

stabilization Yellowness indexafter 5 times extrusion

Control 280.05%Chinox 168 25

0.05% P-EPQ 190.05% Chinox626 12

2010/3/162010/3/16

PPhosphate antioxidant for ABShosphate antioxidant for ABS

Chinox DP

ABS compounding ABS compounding stagestage

Chinox 618Chinox 618 Chinox DPChinox DP Yellow indexYellow index(initial)(initial)

DosageDosage 1000 PPM1000 PPM -- 1212

1000 PPM1000 PPM 350 PPM350 PPM 99

OP H

O

2010/3/162010/3/16

Reactable AntioxidantReactable Antioxidant

Chinox 528

Benefit : -Direct food contact possible-Long term lasting performance- Water borne PU system

O

OH

ROH OHR

Advantage : -Act as a polyol , reactable to carboxylic , isocynate group , used in polyester , urethane system as build in AO without migration

Test result in PVC application

TEST ITEM CHINOX 602L Irganox 245DW

Yellow index -25.14 -17.99Whiteness 63.75 54.22b* Value -8.77 -5.97Heat stability (min.) 24 20

Dosage: 200 ppm as 100% solid in PVC latexAll the value is initial color figure of PVC latex after compounding

Water borne antioxidantWater borne antioxidant

Performance of Chinox1024

Specimen:LDPE communications wire insulationBase antioxidant:0.07% Chinox1076Failure criterion: crack appears

Stabilization Days oven aging at 110℃

control 6 days

0.1% Chisorb 1300 153 days

0.1% Chinox 1024 116 days

2010/3/162010/3/16

New development for PC applicationNew development for PC application

Chinox P-500

Benefit : - Polymer type acrylic resin, with small dosage could improve degradation problem of PC, polyester, which cause dramatically viscosity dropping

Molecular weight , Mn 1 2 3 4 5

0.1% Chinox P-500 52000 53500 51000 48500 46000

Without 52500 51000 48000 42000 38000

Applications of plastic additivesApplications of plastic additives

PVC application 1PVC application 1

UVAUVA-- Flexible PVC: Chisorb 336, BPFlexible PVC: Chisorb 336, BP--12,32012,320-- Rigid PVC : 5411, 327, PRigid PVC : 5411, 327, PAntioxidantAntioxidant-- Chinox 8850Chinox 8850Heat stabilizerHeat stabilizer-- DBM 83DBM 83-- SBM50 ( FDA approval )SBM50 ( FDA approval )

PVC application 2PVC application 2

Polymerization stage :Polymerization stage :-- Suspension or emulsion polymerization , PVC Suspension or emulsion polymerization , PVC

maker will dose antioxidant as chain controller maker will dose antioxidant as chain controller as well as antioxidant.as well as antioxidant.

-- DBC designed Chinox 602L as an emulsified DBC designed Chinox 602L as an emulsified water borne antiwater borne anti--oxidant for this application . Its oxidant for this application . Its performance have been approved in ABS, performance have been approved in ABS, Rubber Latex, and PVC application.Rubber Latex, and PVC application.

PE/PP applicationPE/PP application

General applicationGeneral application: Chinox 1010, 1076,168, : Chinox 1010, 1076,168, Chisorb 5411,770,622,944Chisorb 5411,770,622,944

Agriculture filmAgriculture film : Chisorb 944, 622: Chisorb 944, 622Chisorb 519 for antiChisorb 519 for anti--pesticide and acid rainpesticide and acid rain

Film, FiberFilm, Fiber : Chinox 3114, 1330: Chinox 3114, 1330Crosslinkable PECrosslinkable PE : Chinox 3114, 1330: Chinox 3114, 1330BumperBumper : Chisorb 622, 944, 5411,770: Chisorb 622, 944, 5411,770CableCable : Chinox 1024: Chinox 1024

Polyamide ( Nylon )Polyamide ( Nylon )

•• AO: Chisorb 1098, 168, 1010AO: Chisorb 1098, 168, 1010•• UVA : Chisorb 234, 328, 5431UVA : Chisorb 234, 328, 5431•• HALS : 622, 944HALS : 622, 944•• AntiAnti--NOX : Chisorb 1300/1500NOX : Chisorb 1300/1500

ABS , PC/ABS, PSABS , PC/ABS, PS

•• AO: AO: Chinox 8850Chinox 8850 ,1076, 1010,,1076, 1010, 7 , AO7 , AO--5400 ( polymerization stage ), 5400 ( polymerization stage ), DP, 168, DP, 168, P500 ,P500 ,Chinox 602LChinox 602L

•• UVA: P,5411UVA: P,5411•• HALS : 770HALS : 770

Polyol applicationPolyol application

•• BHT is the most common applied in polyol BHT is the most common applied in polyol synthesis , which is remain in polyol ,and down synthesis , which is remain in polyol ,and down stream product like PU or UP . As BHT is very stream product like PU or UP . As BHT is very easy quench to a quinone , which always cause easy quench to a quinone , which always cause yellowing or pinking .yellowing or pinking .

•• Chinox 35 could solve this problemChinox 35 could solve this problem•• Chinox TPChinox TP--10H, TP10H, TP--10,TP10,TP--80 is designed to 80 is designed to

replace TPP with high temperature resist and replace TPP with high temperature resist and color stabilitycolor stability

PU application 2PU application 2

--Polyether polyol : good hydrolysis, poor Polyether polyol : good hydrolysis, poor weatherability, cheapweatherability, cheap

Chisorb SUV and 5103 are designed to used Chisorb SUV and 5103 are designed to used in polyether polyol PUD to improve in polyether polyol PUD to improve weatherability .weatherability .

These products could be easily emulsfied to These products could be easily emulsfied to PUD formulation ,it is recommended to PUD formulation ,it is recommended to dose in formulation or synthesis stage .dose in formulation or synthesis stage .

PU application 3PU application 3

•• Solvent base PUSolvent base PU : Chisorb 971 covers : Chisorb 971 covers whole range UV absorption with oxidation whole range UV absorption with oxidation protection. protection.

•• Other recommendation : Chisorb P or 328, Other recommendation : Chisorb P or 328, with 292 ,770 or 622 for coating , resin.with 292 ,770 or 622 for coating , resin.

•• TPUTPU : Chisorb B2661: Chisorb B2661

PU application 4PU application 4

•• PU foamPU foam ::Chisorb B2650, SUV both are blend of UV Chisorb B2650, SUV both are blend of UV absorber ,AO and HALS , have full range absorber ,AO and HALS , have full range covering from UVA to UVB , as well as covering from UVA to UVB , as well as protection from oxidation. The excess protection from oxidation. The excess dose of Chinox TPdose of Chinox TP--10 has improving heat 10 has improving heat resistance.resistance.

PU application 5PU application 5

•• SpandexSpandex ::UVA : Chisorb 5103,326, 234 UVA : Chisorb 5103,326, 234 HALS : Chisorb 622HALS : Chisorb 622AntiAnti--gas fading : Chisorb 1300,1500gas fading : Chisorb 1300,1500•• Reactive type AOReactive type AO : Chisorb 528, with 2: Chisorb 528, with 2--OH OH

function remained ,play as an antioxidant and function remained ,play as an antioxidant and polyol could be polymerizable in back borne polyol could be polymerizable in back borne without migration .without migration .

PolyesterPolyester

•• UVA : 327, 326, 5103UVA : 327, 326, 5103•• AO : 1010, 3114AO : 1010, 3114•• Optical brightener : OBOptical brightener : OB--11•• AntiAnti--hydrolysis agent : Chinox Phydrolysis agent : Chinox P--500500

PC applicationPC application

•• UVA: Chisorb 5103 , 5411, 325, 234UVA: Chisorb 5103 , 5411, 325, 234•• AO : Chisorb PAO : Chisorb P--500, 1010, 3114, 1330, 500, 1010, 3114, 1330,

168168