high lights! - virtualpu.comvirtualpu.com/uploads/user_doc_attachment/0-2014-04-08 19:43:27... ·...

High lights!Radiation curing with resins and photoinitiators for industrial coatings and graphic arts: Laromer®, Irgacure®, Lucirin®, Darocur®

EDC_4511_e_BR_Strahlung_korr.indd 1EDC_4511_e_BR_Strahlung_korr.indd 1 19.09.11 14:3019.09.11 14:30

2 High lights!

Radiation curing with resins and photoinitiators for industrial coatings and graphic arts

BASF and the effi ciency of the

radiation-curing resins and photoinitiators 3

BASF - the one stop shop for radiation curing 4 - 5

Products for lifetime “as-new” appearance 6 - 7

Radiation-curable products for

printing and packaging 8 - 9

Radiation curing

Laromer® resins 10 - 17

Product technology overview

Laromer® functional monomers 18 - 19

Technical appendix oligomers

Viscosity - reactivity and hardness – fl exibility 20 - 21

Technical appendix functional monomers

Viscosity - reactivity and hardness - fl exibility 22 - 23

Photoinitiators – a key element of UV technology 24 - 25

Photoinitiator selection guide

Photoinitiators Irgacure®, Darocur®, Lucirin® 26 - 41

Absorption spectra of photoinitiators 42 - 43

Table of content


3High lights!


Introduction

Coatings curable by electron-beam or UV radiation have found many markets in the past fi ve decades. The radiation-curable technology is used in various applications and industry branches such as printing and packaging, automotive and industrial coatings, furniture and fl ooring, adhesives and special applications. The advantages comprised by the technology are obvious such as instant curing, low energy consumption, direct further processing, high scratch and chemical resistance and low volatile organic compound content.

As one of three environmentally friendly technologies, radiation-curable coatings are facing a bright future since they match the legislation requirements to be a “green” technology aside of water-based and powder coatings. UV/EB coatings have had a high growth for many years which is expected to continue.

BASF and the effi ciency of the radiation-curing resins and photoinitiators

Customized-solution provider

BASF continuously works on further product developments to exploit the opportunities in the fi eld of radiation curing. In close cooperation with customers and networking with the whole value chain, BASF supports the innovation drivers in fi nding new solutions for the market needs of today and the challenges of tomorrow.

The customer-oriented scientifi c and technical work at BASF sets standards initiated since the inception of the radiation- curable coatings technology. The technical center offers possibilities to test with up-to-date UV/EB curing equipment and new technologies such as UV-LED. The center also provides different application techniques from spraying to curtain and roller coating as well as test equipment to support our customers in meeting the industry standards and norms. Our technical service is renowned to give excellent advice on coating guidelines, working closely together with coating formulators, equipment and production line manufacturers to develop best solutions for the market requirements.

EDC_4511_e_BR_Strahlung.indd 3EDC_4511_e_BR_Strahlung.indd 3 19.09.11 10:4719.09.11 10:47

BASF – the one stop shop for radiation curing

The unique product portfolio throughout all radiation curable coating components from resins, photoinitiators to additives allows BASF chemists to give excellent advice and to pass on in-depth knowledge about component interactions out of one hand to our partners. Helping our customers to improve their processes and coating properties is our commitment.

High-throughput screening

Substantial investments in the development of new products, testing methods and new high-throughput screening techniques for customer-driven innovations keep us in a front-runner position within the radiation-curing industry.

With our broad and unique product portfolio we meet and exceed the highest market demands. Through our innovative excellence and research competence we set new standards and market trends.

Quality, reliability and consistency

BASF as the chemical company is suffi ciently backward- integrated in the supply chain from the oil well to the fi nal product. Obviously this offers some advantages to our customers which they can not fi nd anywhere else; a secured supply on a constantly high quality level.

Nevertheless, BASF puts continuous efforts into process improvements, new processes and new production technologies to facilitate the high product quality or to improve the already existing high level. Our customers can simply expect more than standard.

The global innovation power inside BASF creates a one-of-a-kind network to satisfy customer demands.

4 High lights!



Prepared for REACH and GHS

Sustainable and ecological acting is one of the key measurements in a global context to preserve our standard of living. As a member in the international Responsible Care®1 initiative and as one of our company’s responsibilities BASF is committed to ecological sustainability. In supporting the legislative authorities world-wide in their efforts to ensure the safety of our environment and the human health we are well prepared for the new safety standards introduced recently. BASF has implemented the new REACH (Registration, Evaluation and Authorisation of Chemicals) and GHS (Global Harmonized System) guidelines in the company’s production and supply chains. Our experts help our customers with the implementation of the new safety standards and give consultancy to our partners if requested.

5High lights!


Innovation and services

In close cooperation with its partners, BASF is developing innovative solutions in analytical and testing challenges. BASF as a solution provider to the industries supplies its customers with several analytical, technical and supply chain services. BASF provides services and technical solutions to a broad range of industries:

• printing and packaging• automotive and industrial coatings• furniture and fl ooring• adhesives• special applications

Sustainability through “green” technologies is a strong demand from end-consumers. BASF´s certifi ed eco analysis gives a tool to customers to calculate the eco friendliness, the environmental impact and comparison of different technologies. The coating industry is facing time-consuming and cost-intensive challenges in developing new coatings with the demanding property profi le of their customers with the variety of available raw materials. Many unknown interactions between the coating components inside a formulation can take place in the development stage. In helping our customers to save time and money in formulation testing, BASF has built up a new high-throughput screening device.


Products for lifetime “as-new” appearanceDiscover the new possibilities

Abrasion resistance

Abrasion resistance is one of the dominating requirements in the world of high-quality fl ooring products. The product of choice depends directly on the test method. Different test methods require different product characteristics. For each test method (Taber®2 Abraser) BASF offers the optimum solution.

Abrasion resistance (Taber®2 Abraser)

Product name S 33 / S 42 Falling sand CS 10 / CS 17

Laromer® PE 56 F

Laromer® PE 9032

Laromer® UA 9065

Laromer® UA 9033

Laromer® PR 9052

Laromer® TMPTA

Laromer® DPGDA

Laromer® LR 8887

Scratch resistance

Many different applications require a highly scratch-resistant coating to assure a long-lasting service life. High-performance automotive clear coats, plastics coatings but also furniture and fl ooring coatings are only a few examples. Highly scratch-resistant surfaces can be achieved via two alternative routes, i. e., either by high-functionality or nano-modifi ed resins.

Product name Scratch resistance Key features

Laromer® LR 8987 hard with excellent weather resistance

Laromer® UA 9048 high functionality, diluted in DPGDA

Laromer® UA 9050 high functionality, diluted in butyl acetate

Laromer® UA 9047 high functionality, physical drying, diluted in butyl acetate

Laromer® PO 9026 contains 50 % nano particles, low viscous

Laromer® TMPTA preferred diluent

6 High lights!



Weather resistance

The outdoor use of UV/EB coatings offers a wide range of different applications for this coating technology. The key to formulating such weather-resistant coatings is the use of aliphatic urethane acrylates in combination with the right photoinitiator cocktail.

Product name Hard / scratch-resistant Flexible

Laromer® LR 8987

Laromer® UA 9029

Laromer® UA 9048

Laromer® UA 9050

Laromer® UA 19 T

Laromer® UA 9028

Laromer® UA 9033

To achieve the best possible weather resistance, please ensure that appropriate performance light stabilizers are used in your coating formulations.. For this purpose BASF offers the Tinuvin® product range (UV absorbers and HALS).

7High lights!


Adhesion

Many of the latest UV/EB applications are on metal or plastic substrates. These non-absorbing substrates require the careful selection of radiation-curable raw materials in order that the coatings formulation achieves the necessary adhesion performance. This can be achieved by use of a dual-cure resin, control of fi lm shrinkage (reduction of stress within the fi lm), optimization of substrate wetting or the use of an acidic adhesion promoter.

Product name Metal Plastics Wood

Laromer® UA 9059

Laromer® PA 9039

Laromer® PA 9083

Laromer® LR 9000

Laromer® UA 9033

Laromer® UA 9072

Laromer® LR 9013

Laromer® TBCH

Laromer® LR 8887

Laromer® POEA

Liquid NVC

excellent very good good


Radiation-curable products for printing and packaging

excellent very good good - not suitable

Laromer® Offset inks Flexo inks Screen inks Overprintvarnish

universal grinding resins

LR 9013

LR 8985

polyester acrylates

LR 9004

PE 56 F

PE 9024

PE 44 F

PE 9074

PE 9079

polyether acrylates (free of monomers, amine-modified)

PO 77 F

PO 94 F

LR 8869

LR 8996

oligoether acrylates

LR 9007

PO 43 F

PO 33 F

LR 8863

epoxy acrylates (aliphatic)

LR 8765 -

Laromer® Offset inks Flexo inks Screen inks Overprintvarnish

epoxy acrylates (aromatic)

LR 9019

LR 9023

LR 8986

urethane acrylates (aliphatic, with monomer)

UA 19 T

UA 9033

LR 8987

specialties

PA 9039 improves adhesion to plastics and metal

PA 9083 improves adhesion to plastics and metal

LR 9000 adhesion primer on plastic substrates

PO 9026 improves scratch resistance in OVP, inks

reactive diluents

TPGDA

DPGDA

HDDA

TMPTA

POEA -

TBCH -

8887 -

8 High lights!



9High lights!



Radiation curing Laromer® resins

10 High lights!


Laromer ® Type of resin Type of thinner[content]

Functionalitycalculated

Viscosity[Pa·s, 23 °C]

Hydroxyl value [mg KOH/g]

DIN EN ISO 4629Hardness Elasticity

epoxy acrylates

LR 8765 aliphatic none 2.0 0.6 - 1.2 330

LR 8986 aromatic none 2.4 3 - 6 170

LR 9019 aromatic none 2.4 12 - 20 175

LR 9023 aromatic DPGDA (15 %] 2.4 2 - 5 150

polyester acrylates

PE 55 F none 3.1 25 - 45 70

PE 56 F none 3.1 20 - 40 70

PE 46 T TPGDA [30 %] 2.8 2 - 2.5 60

LR 9004 none 2.6 20 - 50 60

PE 9024 none 2.6 10 - 30 70

PE 9045 TPGDA [20 %] 2.5 2 - 7 60

PE 44 F none 3.0 2 - 5 80

LR 8800 none 3.0 4 - 8 80

LR 8907 DPGDA [25 %] 1.9 0.5 - 2 120

LR 8981 none 3.0 4 - 14 80

PE 9032 modified none 4.0 15 - 25 50

PE 9074 none 3.2 7 - 13 50new

PE 9079 none 3.4 2 - 4 @ 60 ºC 60new

PE 9084 none 3.3 16 - 26 70new


excellent good medium low

11High lights!


Reactivity Chemicalresistance Characteristics Europe

EINECSUSATSCA

CanadaDSL

JapanENCS

ChinaIECSC

KoreaECL

partially water-soluble, fl exible, highly reactive

low viscosity, free of diluents, very good chemical resistance

highly reactive, very good chemical resistance - - -

diluted version of Laromer® LR 9019 - - -

well-balanced properties with high toughness

improved compatibility with reactive diluents (versus PE 55 WN)

lowly viscous, diluted version of Laromer® PE 56 F

tough with good adhesion, good chemical resistance - - -

compatible with nitrocellulose - - -

lowly viscous version of Laromer® LR 9004 - - -

free of diluents, low viscosity, low odor, fl exible - -

hard, chemical resistance, low odor -

highly fl exible, use in combination with hard, less fl exible binders - - - -

highly reactive with good sanding properties - - -

abrasion-resistant in parquet applications (“falling sand”) - - - -

good adhesion, tough, reactive, resistant to chemicals - -

highly viscous version of Laromer® PE 9074 - -

medium viscous version of Laromer® PE 9074 - -



12 High lights!





Hydroxyl value [mg KOH/g]


polyether acrylates

PO 33 F alkoxylated TMP triacrylate none 3.0 0.07 - 0.13 30

LR 8863 ethoxylated TMP triacrylate none 3.0 0.05 - 0.1 10

GPTA propoxylated glycerin triacrylate none 3.0 0.07 - 0.13 30new

PO 43 F none 2.4 0.2 - 0.4 100

LR 8967 none 2.6 0.12 - 0.19 50

LR 8982 none 2.7 0.15 - 0.3 70

LR 9007 none 4.0 0.8 - 1.5 130

amine-modifi ed polyether acrylates

PO 77 F none 2.9 1 - 3 120

PO 9067 none 2.8 0.4 - 0.7 50new

PO 84 F none 3.5 0.4 - 0.7 50

PO 94 F none 3.5 0.3 - 0.6 55

LR 8997 none 3.4 0.3 - 0.5 55

PO 83 F none 2.8 0.09 - 0.13 30

LR 8889 none 2.6 0.09 - 0.14 60

LR 8869 none 2.8 0.06 - 0.11 30

LR 8996 none 2.9 0.05 - 0.09 30


excellent good medium low SNUR = signifi cant new use rule

13High lights!



EINECSUSATSCA

CanadaDSL

JapanENCS

ChinaIECSC

KoreaECL

low yellowing, low-odor diluent SNUR - -

lower in viscosity than Laromer® PO 33 F

more hydrophobic than Laromer® LR 8863

chemical resistance, allround resin

lowly viscous version of Laromer® PO 43 F

partially water-soluble (spray viscosity adjustable) - -

lowest amount of extractables, scratch-resistant - -

reactive allround resin, good sanding properties - - -

reactive, good substrate wetting - - -

reactive, good pigment wetting SNUR - -

highly reactive, very good chemical resistance -

highly reactive, very low in color - - - -

good chemical resistance, low viscosity SNUR - - -

reactive, low viscosity, fl exible - - -

harder than Laromer® LR 8889 - - -

reactive, very low color and viscosity - - -





Hydroxyl value[mg KOH/g]


urethane acrylates

UA 19 T aliphatic TPGDA [35 %] 2.0 14 - 32 10

UA 9028 aliphatic butyl acetate [30 %] 2.0 0.8 - 1.6 15

UA 9030 aliphatic Laromer® LR 8887 [30 %] 1.7 80 - 150 12

LR 8987 aliphatic HDDA [30 %] 2.3 4 - 6 11

UA 9029 aliphatic butyl acetate [30 %] 2.4 0.3 - 1 5

UA 9033 aliphatic Laromer® LR 8887 [30 %] 1.7 15 - 25 6

UA 9047 aliphatic butyl acetate [30 %] > 6.0 2 - 7 10

UA 9048 aliphatic DPGDA [25 %] 6.5 10 - 20 10

UA 9050 aliphatic butyl acetate [20 %] 8.0 1.5 - 5 10

UA 9072 aliphatic TBCH [30 %] 1.7 2-15 / 60 °C 6new

UA 9065 aromatic DPGDA [35 %] 2.0 7 - 9 5

UA 9073 aromatic - 2.0 2-15 / 60 °C, 9new

water-based

PE 22 WN polyester acrylate water [50 %] 2.2 0.15 - 0.5 -

PE 55 WN polyester acrylate water [50 %] 2.2 0.25 - 0.65 -

LR 8949 aliphatic urethane acrylate dispersion water [60 %] 1.7 0.015 - 0.18 -

LR 8983 aromatic urethane acrylate dispersion water [60 %] 0.7 0.05 - 0.3 -

LR 9005 aromatic urethane acrylate dispersion water [60 %] 2.0 0.02 - 0.25 -

UA 9060 aromatic urethane acrylate dispersion water [60 %] 2.0 0.005 - 0.3 -

UA 9064 urethane acrylate dispersion water [62 %] - 0.02 - 0.25 -new

WA 9057 acrylic UV dispersion water [64 %] - 0.01 - 0.2 -

UA 9059 aliphatic urethane acrylate water [30 %] 1.8 6 - 11 -


14 High lights!




EINECSUSATSCA

CanadaDSL

JapanENCS

ChinaIECSC

KoreaECL

elastic, low yellowing, fl exible at temperatures below O °C -

highly elastic, low yellowing, lowly viscous, monomer-free -

highly elastic, low yellowing, good adhesion - -

scratch- and weather-resistant, for outdoor applications - - - -

monomer-free version of Laromer® LR 8987 - - - -

highly elastic, reactive, good adhesion, low shrinkage - -

physical drying, best performance when UV-cured at high temparature - - - - -

excellent scratch and abrasion resistances, highly functional - - -

lowest yellowing, excellent scratch resistance - - -

extremely flexible, best strain-stress behavior - - - - -

very reactive, very fl exible, good abrasion resistance (“falling sand”) - - - - -

fl exible and tough with high viscosity

hard, excellent chemical resistance, good sanding properties - -

fl exible, easy to matt, adhesion to PVC - -

good grain enhancement, very good chemical and weather resistances - - - -

excellent physical-drying properties, easy to formulate - - -

excellent scratch and chemical resistances -

very good chemical and scratch resistances, fast drying, very hard - - -

low-yellowing version of Laromer® UA 9060 - - - - -

good chemical and scratch resistances, excellent block resistance - - - -

excellent adhesion on wood, very fl exible, excellent coin test results - - - - -

15High lights!


excellent good medium low






Hydroxyl value[mg KOH/g]


special radiation-curable products

UP 35 D unsaturated polyester DPDGA [45 %] 3.5 3 - 6 -

LR 9013 modifi ed polyether acrylate none 3.0 45 - 70 25

LR 8985 modifi ed polyether acrylate none 3.0 60 - 80 25

PO 9026 nano-modifi ed polyether acrylate none 1.5 0.6 - 1.5 -

PR 9052 TMPTA [60 %] 6.0 4 - 8 -

PR 9058 modifi ed aromatic none 2.3 3 - 6 170

PA 9039 adhesion promoter none 1.5 0.3 - 0.8 -

PA 9083 adhesion promoter none 1.0 1.2 - 3.5 -new

dual-cure product

LR 9000 aliphatic urethane acrylate none 2 + 2 NCO 1 - 1.4 -

16 High lights!




EINECSUSATSCA

CanadaDSL

JapanENCS

ChinaIECSC

KoreaECL

hard, good chemical resistance, good sanding properties - - -

excellent pigment wetting properties, low in shrinkage

more hydrophobic than Laromer® LR 9013 SNUR -

contains 50 % nano particles, very good scratch resistance -

abrasion-resistant in fl ooring application (S42, S33), hard, scratch-resistant -

excellent pigment wetting, good fi ller acceptance, low viscosity

leads to good adhesion on different substrates -

co-binder to increase adhesion on metal and plastic

contains NCO- and UV-reactive groups within one molecule -

excellent good medium low SNUR = signifi cant new use rule

17High lights!



Product technology overview Laromer® functional monomers

Product name Structure CAS number

Mol mass[g/mol]approx.

Density[g/cm3]

Laromer® functional monomers

Laromer® TMPTAtrimethylolpropane triacrylate 15625-89-5 300 1.102 (25 °C)

Laromer® BDDAbutanediol diacrylate 1070-70-8 200 1.049 (45 °C)

Laromer® HDDAhexanediol diacrylate 13048-33-4 230 1.015 (25 °C)

Laromer® TPGDAtripropyleneglycol diacrylate 42978-66-5 300 1.036 (25 °C)

Laromer® DPGDAdipropyleneglycol diacrylate 57472-68-1 240 1.046 (25 °C)

Laromer® POEAphenoxyethyl acrylate 48145-04-6 190 1.100 (25 °C)

Laromer® LR 8887trimethylolpropaneformal monoacrylate

66492-51-1 200 1.094 (25 °C)

Laromer® TBCH4-t-butylcyclohexyl acrylate

84100-23-2282-104-8 210 0.940 (25 °C)

lauryl acrylate 1214 2156-97-0 250 0.870 (25 °C)

ethyldiglycol acrylate 7328-17-8 188 1.006 (25 °C)

4-HBA4-hydroxybutyl acrylate 2478-10-6 144 1.04 (25 °C)

NVCN-vinyl caprolactamalso available in liquid form

2235-00-9 139 1.01 (40 °C)

DVE-3Triethyleneglycol divinyl ether 765-12-8 202 99 (25 °C)

(CH2)4 OH

CH2=CH-N

H2C==CH–O–CH2––CH2–O–CH2––CH2–O–CH2––CH2–O–CH==CH== 2

18 High lights!



Content of stabilizer[Me HQ]

Color [APHA DIN ISO 6271]

Viscosity[mPa·s, 23 °C]

approx.

EuropeEINECS

USATSCA

CanadaDSL

JapanENCS

ChinaIECSC

KoreaECL

200 ± 50 ppm max. 150 130

200 ± 50 ppm max. 150 5

200 ± 50 ppm max. 150 6

350 ± 50 ppm max. 150 11

350 ± 50 ppm max. 150 8

200 ± 50 ppm max. 250 8

1000 ± 100 ppm max. 200 40 - -

200 ± 50 ppm max. 100 9 - -

200 ± 50 ppm max. 150 6

2000 ± 200 ppmstabilizer blend max. 250 5

max. 50 12 -

max. 50 3 -

max. 50 3 -

19High lights!



Technical appendix oligomers Viscosity – reactivity and hardness – fl exibility

Viscosity – reactivity / all products were cured with 1 UV lamp 120 W/cm. Initiator: 4 % Irgacure® 500

PO 77F

LR 8981

LR 9019

UA 9065

LR 9023

UA 9050

LR 8987

UA 9048

UA 9047

PE 9045

UA 9060WA 9057

UA 9059

PA 9039

PR 9058

PE 22 WN

LR 8983PO 83F

LR 8863

LR 8949LR 9005

PO 33 F

PO 43 FLR 8982LR 8967

LR 8907

PO 9026UA 9028

PR 9052

LR 8800

LR 8986UP 35 D

PE 46 T

LR 8765

PE 44 F

LR 9007

PE 56 F

PE 55 FLR 9004

UA 9033PE 9024

PE 9032UA 19 T

LR 9013

LR 8985

UA 9030

LR 8869

PE 55 WN

PO 84 F

LR 8889

LR 8996

UA 9029

LR 8997

PO 94 F

0 10 20 30 40 50 60 70 80 90

1,000,000

100,000

10,000

1000

100

10

1

viscosity [mPa·s]

reactivity [m/min]

epoxy acrylates

amine-modified polyether acrylates

polyester acrylates water-based products


urethane acrylates polyether acrylates

PE 9074

UA 9072

UA 9064

UA 9073

PE 9079

GPTA

PO 9067

PE 9084

20 High lights!



Hardness – flexibility / all products were cured 5 x 5 m/min with 1 UV lamp 120 W/cm. Initiator: 4 % Irgacure® 500

UA 9048UA 9050

PE 9045

UA 9047

UA 9065

PA 9039

PR 9058

PR 9052

LR 8863

PO 9026

LR 8985

PO 33 F

LR 8967

PO 43 F

LR 9007

LR 8986

LR 8949

PE 22WN

LR 9019

UA 9029

UP 35 D

PE 9032

PO 94 F

LR 8996

LR 8869

PO 83 F

LR 8765

LR 8889 LR 8997

PO 77 F

PE 46 TPE 44 F

LR 8981

PE 55 F

PE 56 F

PE 55 WNLR 9004

LR 8907

PE 9024

UA 19 T

LR 9005

UA 9060

LR 8983

LR 9023

PO 84 FLR 8982

LR 9013

PE 9074

PE 9079

GPTA

PO 9067

PE 9084

UA 9059

LR 8800

UA 9030

UA 9033

UA 9028

LR 8987

0 20 40 60 80 100 120 140 160

10

9

8

7

6

5

4

3

2

1

0

Erichsen indentation [mm]

pendulum hardness [oscillations]

epoxy acrylates

amine-modified polyether acrylates

polyester acrylates water-based products


urethane acrylates polyether acrylates

WA 9057

UA 9072

UA 9073

UA 9064

21High lights!



Technical appendix functional monomers Viscosity – reactivity and hardness – fl exibility

Monomers: viscosity – reactivity / formulation: 70 parts Laromer® PE 56 F, 30 parts monomer, 4 parts Irgacure® 500

7,000

6,000

5,000

4,000

3,000

2,000

1,000

0

TM

PTA

BD

DA

HD

DA

TP

GD

A

DP

GD

A

PO

EA

LR

88

87

TB

CH

LA

12

14

*

ED

GA

4-H

BA

NV

C

DV

E-3

viscosity [mPa·s]

20.0

18.0

16.0

14.0

12.0

10.0

8.0

6.0

4.0

2.0

0

reactivity [m/min]

* -only 10 parts

22 High lights!



Monomers: hardness – flexibility / formulation: 70 parts Laromer ® PE 56 F, 30 parts monomer, 4 parts Irgacure® 500

70

60

50

40

30

20

10

0

9

8

7

6

5

4

3

2

1

0

pendulum hardness Erichsen indentation [mm]

TM

PTA

BD

DA

HD

DA

TP

GD

A

DP

GD

A

PO

EA

LR

8887

TB

CH

LA

1214*

ED

GA

4-H

BA

NV

C

DV

E-3

* -only 10 parts

23High lights!



Photoinitiators – a key element of UV technology

UV-curing is one of the most rapidly growing technologies within the coatings, printing and packaging, adhesives and electronic materials as well as related industries. UV-curing systems have been used to dramatically increase line speeds and develop environmentally friendly coatings.

Perfect partner for UV-curable resins

Aside of the careful selection of the UV resin, the selection of the correct photoinitiator or photoinitiator combination is critical to achieve the desired curing speed and balance of properties.

UV-cured inks are used for variety of lithographic, fl exographic and screen-printing applications. These inks present special formulation challenges due to their pigmentation and need for tightly controlled viscosity. To solve this problem, BASF introduced several photoinitiators such as Irgacure® 369 and Irgacure® 379 with strong absorption at longer wavelength in the UV region. Therefore, they are very effective in curing cyan and black inks. These photoinitiators may be used alone or in combination with sensitizers. Generally a photoinitiator concentration of 1 - 5 % is suggested with ladder studies

to optimize the formulation in terms of reactivity. Irgacure® 369 may impart color to the ink due to the absorption of visible light. This makes it less preferable for white, pastel and other light-color inks. For this segment, a photoinitiator of the bisacyl phosphine oxide (BAPO) class is suggested. Irgacure® 819 shows high reactivity due to a long-wavelength absorption in combination with effi cient photobleaching.

For UV-cured coatings, products of the ɑ-hydroxyketone family (Irgacure® 184, Irgacure® 2959, Irgacure® 127, Darocur® 1173) are preferred as part of a photoinitiator package when curing unpigmented clear coatings or for surface curing in highly pigmented systems. For through curing of thicker sections and for highly pigmented systems, an acylphospine oxide type of photoinitiator such as the BAPO

24 High lights!



and monoacyl phospine oxide (MAPO) families is suggested. BAPO-type photoinitiators are especially designed to be activated by longer-wavelength UV light in the near-visible region above 400 nm. Light of this wavelength penetrates deeper into the lower layers of the coating, thus enabling the through curing desired. Shorter-wavelength light, around 230 nm, is of higher photon energy but is less penetrating than that of longer wavelengths. Light of this shorter wavelength is particularly useful for surface curing. Moreover, BAPO-type photoinitiators also allow UV absorbers to be formulated into the coating for improved outdoor durability. In addition to excellent through-cure properties, BAPO phototinitiators photobleach after UV exposure to give a clean white appearance in contrast to an off-white color associated with other long-wavelength absorption photoinitiators.

Selection of the best individual photoinitiator or combination depends on a number of variables including the chemistry of the resins system (UPES, epoxy acrylate, urethane acrylate), selection of monomers, UV lamp type and orientation, curing speed required, coating properties, substrate and many more.

25High lights!



Photoinitiator selection guide Photoinitiators Irgacure®, Darocur®, Lucirin®

Product name Clear wood coating

Pigmented wood

coating

Clear plastics/

metal

Pigmented plastics/

metal

UV-stabilized clear coatings

Powder coatings

Overprint varnish Offset inks Flexo inks Screen

inks

α-hydroxyketone

Irgacure® 184

Darocur® 1173

Irgacure® 127

Irgacure® 2959

Irgacure® 500

phenylglyoxylate

Irgacure® 754

Darocur® MBF

acylphosphine oxide

Lucirin® TPO

Lucirin® TPO-L

Irgacure® 2100

Irgacure® 819

Irgacure® 819-DW

Darocur® 4265

Irgacure® 2022

α-aminoketone

Irgacure® 907

Irgacure® 369

Irgacure® 379

Irgacure® 389new

26 High lights!



Electronic coatings, adhesives and photoresists for displays, micro devices, circuit

boards and offset plates

Near-UV exposure

UPES* systems

Acrylated systems

Cationic polymerization

Photoacid-catalyzed systems

Water-based UV

formulations

Low volatility, low odor

Non-yellowing High purity High

stability

very well suited well suited suited * unsaturated polyesters

27High lights!




Product name Clear wood coating

Pigmented wood

coating

Clear plastics/

metal

Pigmented plastics/

metal

UV-stabilized clear coatings

Powder coatings

Overprint varnish Offset inks Flexo inks Screen

inks

benzophenone (BP)

Darocur® BP

benzildimethyl ketal

Irgacure® 651

sulfonium salts

Irgacure® 250

Irgacure® 270

Irgacure® PAG 290

Irgacure® GSID 26-1

other

Irgacure® 784

oxime esters

Irgacure® OXE 01

Irgacure® OXE 02

photoacid generators

Irgacure® PAG 103

Irgacure® PAG 121

Irgacure® PAG 203

Irgacure® CGI 1380

Irgacure® CGI 1907

Irgacure® CGI 725

28 High lights!



Electronic coatings, adhesives and photoresists for displays, micro devices, circuit

boards and offset plates

Near-UV exposure

UPES* systems

Acrylated systems

Cationic polymerization

Photoacid-catalyzed systems

Water-based UV

formulations

Low volatility, low odor

Non-yellowing High purity High

stability

/

very well suited well suited suited * unsaturated polyesters

29High lights!




Product name Chemical name Structure

α-hydroxyketone

Irgacure® 184 1-hydroxy-cyclohexyl-phenyl-ketone

Darocur® 1173 2-hydroxy-2-methyl-1-phenyl-1-propanone

Irgacure® 127 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one

Irgacure® 2959 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone

Irgacure® 500 Irgacure® 184 (50 %), benzophenone (50 %)

phenylglyoxylate

Irgacure® 754 oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester

Darocur® MBF phenyl glyoxylic acid methyl ester

C

O

OHOOH

CC

O

O

O

C

O

OH

30 High lights!



Appearance UV/VIS absorption peaks [nm] Solubility Key properties

solid 246, 280, 333 low yellowing, medium volatility, highly effi cient for surface-curing

liquid 245, 280, 331 with good solvent properties, highly suitable for blends with other photoinitiators, highly effi cient for surface curing, slightly more reactive than Irgacure® 184

solid 260, 320 superior reactivity over Irgacure® 184 or Darocur® 1173, low sensitivity to oxygen inhibition, low emission/odor after curing

solid 276,331 low yellowing, low odor, low volatility, low migration, reactive OH group enabling use as building block, FDA-approved for indirect food contact in adhesive applications

liquid 250, 332 low yellowing, low viscosity provides advantage lowering the viscosity of formulation, highly effi cient for surface curing, synergistic effect with amines

liquid 260, 345 highly effi cient in surface curing, low emission, low residual odor, lowest yellowing after curing

liquid 255, 325 low yellowing after curing/aging, excellent surface-curing properties (stain resistance), allows development of clearcoat with superior adhesion

good solubility medium solubility low solubility

31High lights!




acylphosphine oxide

Lucirin® TPO 2,4,6-trimethylbenzoyl-diphenylphosphine oxide

Lucirin® TPO-L 2,4,6-trimethylbenzoyl-diphenyl phosphinate

Irgacure® 2100 liquid blend of acylphosphine oxides

Irgacure® 819 bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide

Irgacure® 819 DW Irgacure® 819 (45% active) dispersed in water

Darocur® 4265 Lucirin® TPO (50 % by weight)Darocur® 1173 (50 % by weight)

Irgacure® 2022 Irgacure® 819 (20 % by weight)Darocur® 1173 (80 % by weight)


C

O

P

O

C P C

P OC

O O

32 High lights!




solid 295, 380, 393 good solubility in common UV systems, lower through-curing performance than Irgacure® 819low yellowing, low odor

liquid 242, 280, 370 easy to incorporate, low yellowing, photosensitivity at longer wavelength

liquid 275, 370 limited yellowing after curing, improved through-curing and reactivity over Lucirin® TPO, photosensitivity at longer wavelength

solid 360, 365, 405 low odor, low volatility, photosensitivity at longer wavelength

liquid 360, 365, 405 easy to incorporate into water-based UV systems, low odor, low volatility, photosensitivity at longer wavelength

liquid 240, 290, 380 good solubility in common UV systems, Darocur® 4265 can be incorporated into water-based systems, photosensitivity at longer wavelength

liquid 246, 282, 370 lower through-curing performance than Irgacure® 819, well balanced ratio of surface and through-curing, lower degree of photobleaching, photosensitivity at longer wavelength


33High lights!





other

Irgacure® 784titanocene radical initialtortitanium, bis ( ƞ5-2,4-cyclopentadien-1-yl)bis [2,6-difl uoro-3-(1H-pyrrol-1-yl)phenyl]-

oxime esters

Irgacure® OXE 01 oxime ester radical initiator[1-(4-phenylsulfanylbenzoyl)heptylideneamino]benzoate

Irgacure® OXE 02 oxime ester radical initiator[1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate

F

TiF

N

F

F

N

NS

N

O

N

O O

34 High lights!




solid 397, 465 effi cient radical photoinitiator for near UV-A, LED and laser exposure

solid 327 non-yellowing highly reactive near-UV radical photoinitiator for color fi lters, resin black matrix and other display applications

solid 375 only slightly yellowing highly reactive near-UV radical photoinitiator for color fi lters, resin black matrix and in other display applications


35High lights!





α-aminoketone

Irgacure® 907 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one

Irgacure® 369 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1

Irgacure® 379 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one

Irgacure® 389 modifi ed α-aminoketone

benzophenone (BP)

Darocur® BP benzophenone

benzildimethyl ketal

Irgacure® 651 2,2-dimethoxy-1,2-diphenylethan-1-one

C

O

C

O

O

O

CO

S N O

N C

O

NO

N C

O

NO

36 High lights!




solid 232, 240, 307 highly effi cient

solid 233, 324 highly effi cient

solid 237, 320 highly effi cient, excellent solubility compared to Irgacure® 369, easy to incorperate

solid 210, 235, 320 providing excellent through-curing properties along with high reactivity

solid 256, 340 low initial yellowing, low oxygen inhibition, performance can signifi cantly be improved in combination with amine synergists

solid 254, 337 yellowing after curing tends to limit use to primers or intermediate coats


37High lights!





onium salts

Irgacure® 250 iodonium, (4-methylphenyl)[4-(2-methylpropyl) phenyl]-, hexafl uorophosphate(1-)

Irgacure® 270 sulfonium salt cationic initiator

Irgacure® PAG 290 tetralis(2,3,4,5,6-pentafl uorophenyl)boranuide;tris[4-(4-acetylphenyl)sulfanylphenyl]sulfonium

Irgacure® GSID 26-1 tris[4-(4-acetylphenyl)sulfanylphenyl]sulfonium;tris(trifl uoromethylsulfonyl)methide

S+

S

O

S

O

S

O

CS

O

O

F

FF

SOO

FFF

SO

O

F

FF

I+ PF6

-

S+

R1

R1

R1

R

R R

R

R R

PF6-

S+

B–

F

F

F

F

F

F

F

F

F

F

FF

F

F F

FF

F

F F

S

SS

38 High lights!




liquid 240 for curing of thick and highly pigmented cationic systems

solid 242, 327 very low odor during curing and very low migration make the product especially well suitable for food packaging applications

solid 293, 318 high reactivity, for near-UV curing of thick cationic systems, 3D prototyping, LED curing, long pot life

solid 293, 318 high reactivity, for near-UV curing of thick cationic systems, LED curing, long pot life


39High lights!





photoacid generators

Irgacure® PAG 103 oxime sulfonate



Irgacure® CGI 1380 oxime sulfonate



S

N

FF

F

S

N

FF

F

O

N

S

NO S

O

O

F

FF

FFSO

ON

FF

F

F

FF

FF H

OF

FF

F

O SO

O

N

N

O

N

S

NO S

O

O

N

S

NO S

O

O

40 High lights!




solid 418 non-ionic photoacid generator for near-UV and longer wavelengths generating alkyl sulfonic acid

solid 406 non-ionic photoacid generator for near-UV and longer wavelengths generating alkyl sulfonic acid

solid 281 non-ionic photoacid generator for deep-UV generating alkyl sulfonic acid

solid 400 non-ionic photoacid generator for near-UV generating camphor sulfonic acid

solid 200, 240, 255 non-ionic photoacid generator for deep-UV generating nonafl ic acid

solid 323 non-ionic photoacid generator for near-UV generating alkyl sulfonic acid


41High lights!



Absorption spectra of photoinitiators

High lights!


α-hydroxyketone photoininitiators 0.001 % in acetonitrile

α-aminoketone photoinitiators 0.001 % in acetonitrile

acylphosphine oxide photoininitiators 0.1 % in acetonitrile

wavelength [nm]

200 220 240 260 280 300 320 340

1.2

1.0

0.8

0.6

0.4

0.2

0.0

Irgacure® 184 Irgacure® 127 Darocur® 2959 Darocur® 1173

ab

so

rba

nc

e

wavelength [nm]

200 220 240 260 280 300 320 340 360 380

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0

Irgacure® 369 Irgacure® 907 Irgacure® 389

ab

so

rba

nc

e

wavelength [nm]

300 320 340 360 380 400 420 440 460

3.0

2.5

2.0

1.5

1.0

0.5

0.0

Irgacure® 819 Irgacure® 2100 Lucirin® TPO Lucirin® TPO-L

ab

so

rba

nc

e42


Classical photoinitiators 0.001 % in acetonitrile Oxime esters 0.001 % in acetonitrile

Cationic photoinitiators 0.05 % in acetonitrile

wavelength [nm]

200 220 240 260 280 300 320 340

Darocur® MBF Irgacure® 754 Irgacure® 500

Darocur® BP Irgacure® 651

1.2

1.0

0.8

0.6

0.4

0.2

0.0

ab

so

rba

nc

e

wavelength [nm]

200 225 250 275 300 325 350 375 400

Irgacure® 250 Irgacure® 270

2.0

1.5

1.0

0.5

0.0

ab

so

rba

nc

e

wavelength [nm]

200 240 280 320 360 400

Irgacure® OXE 01 Irgacure® OXE 02

1.2

1.0

0.8

0.6

0.4

0.2

0

ab

so

rba

nc

e

43High lights!



ED

C 4

511

e

Contact worldwide

AsiaBASF East Asia Regional Headquarters Ltd. 45/F, Jardine House No. 1 Connaught Place Central Hong Kong Tel.: +852 2731-0111 Fax: +852 2731-5633

EuropeBASF SEResins & AdditivesE-EDC/RA – J 55067056 LudwigshafenGermanyTel.: +49 621 60-49923Fax: +49 621 60-6649923

Eastern Europe, Africa, West AsiaBASF SEBusiness ManagementDispersions & PigmentsEUM/SD – Europe House67056 LudwigshafenGermanyTel.: +49 621 60-76246Fax: +49 621 60-76115

North AmericaBASF CorporationResins & Additives1609 Biddle AvenueWyandotte, MI 48192USATel.: +1 800 231-7868Fax: +1 800 [email protected]

MexicoBASF Mexicana S.A. de C.V.Av. Insurgentes Sur 975Col. Ciudad de los Deportes03710 Mexico, D.F.MexicoTel.: +52 55 5325-2787 +52 55 5325-2687Fax: +52 55 5611-4897

South AmericaBASF S.A.Av. Faria Lima 3600 – 10° andarItaim Bibi – São Paulo – SP 04538-132BrazilTel.: +55 11 3043-3637Fax: +55 11 3043-3110

BASF SE

67056 Ludwigshafen Germany www.basf.com/resins

The data contained in this publication are based on our current knowledge and experience. In view of the many factors that may affect processing and application of our product, these data do not relieve processors from carrying out their own investigations and tests; neither do these data imply any guarantee of certain properties, nor the suitability of the product for a specifi c purpose. Any descriptions, drawings, photographs, data, proportions, weights, etc. given herein may change without prior information and do not constitute the agreed contractual quality of the product. The agreed contractual quality of the product results exclusively from the statements made in the product specifi cation. It is the responsibility of the recipient of our product to ensure that any proprietary rights and existing laws and legislation are observed. When handling these products, advice and information given in the safety data sheet must be complied with. Further, protective and workplace hygiene measures adequate for handling chemicals must be observed.

® = registered trademark of the BASF Group ®1 = Responisble Care is a service mark of the American Chemistry Council ®2 = registered trademark of Taber Acquisitions Corporation


high lights! - virtualpu.comvirtualpu.com/uploads/user_doc_attachment/0-2014-04-08 19:43:27... ·...

Documents