Leather, Feed, Food / Pharma

FORMALDEHYDE AND LEATHERINNOVATIVE FORMALDEHYDE-FREE FILLERS

Smit & Zoon

The Netherlands

v1.3

• Background of formaldehyde

• Formaldehyde in leather chemicals

• Free and releasable formaldehyde

• Hydrolysis of formaldehyde

• Test methods in the leather industry

• Application of leather chemicals

• Introduction to three newly developed products

free of formaldehyde

AGENDA

• What is ‘formaldehyde’?

• A gas

• Well-soluble in water

• Very reactive

BACKGROUND OF FORMALDEHYDE

== OO

HH

HH

CC

• Why use ‘formaldehyde’?

• Conserving• Very good building block in nature and chemistry

• Bulk raw material

• Why on RSL (Restricted Substances Lists)?

• Toxic/irritating• Carcinogenic

• Allergic contact eczema

• Free formaldehyde• Free formaldehyde has no bonds with the leather or the chemicals

• Most phenol syntans and amino resins contain < 10 ppm free formaldehyde

• Some phenol syntans and amino resins are able to release formaldehyde under specific conditions

FREE AND RELEASABLE FORMALDEHYDE

• Releasable formaldehyde• Releasable formaldehyde is chemically bound but can be released due to

hydrolysis. After that it is present as free formaldehyde, finally is released into the air. Then the process starts again with a new resin molecule. The hydrolyzing of the formaldehyde molecules will continue until the source is completely decomposed

• The formaldehyde problems in leather are caused by the releasable formaldehyde

FR

EE

AN

D R

ELE

AS

AB

LE

FO

RM

ALD

EH

YD

E -

SO

UR

CE

S

0

0,2

0,4

0,6

0,81

1,2

formaldehyde/blends

oxazolidine

resins

fixingagents

dyepenetrator

preservatives

dyestuffs

syntans

vegetabletannins

polymers

fatliqours

surfactants

Possible formaldehyde emission

Ve

ry

hig

h

Ve

ry

low

HYDROLYSES OF FORMALDEHYDE

Gas

Gas

-- OHOHCHCH22

-- OHOHCHCH22

-- OHOHCHCH22irreversibleirreversible

Leath

er

or

po

lym

er

Leath

er

or

po

lym

er

-- OHOHCHCH22

-- OHOHCHCH22

reversible

== OOHH

HHCC

== OOHH

HHCC

Formaldehyde

EXAMPLE OF A RSL LISTING (SHOE LEATHER)

FORMALDEHYDE EMISSION – AUTOMOTIVE LEATHER

Test method Limit Remark

VW-

Group

PV 3925 =

VDA 275 10 mg/kg Emission

Daimler DIN 53 315 10 mg/kg Content

BMW GS 97014-3 50 mg/kg

Emission

chamber

test

ISO-DIS 17226-3

Japan LAW 112

EN ISO14184-2

EN ISO14184-1

LGR-TEGEWAISO 27587

VDA 275

DIN 53315-BISO 17226-1

DIN 53315-AISO 17226-2

FormerlyMethod

TEST METHODS IN LEATHER INDUSTRY

Automotivexx√ISO-DIS 17226-3

√xxJapan LAW 112

√xxEN ISO14184-2

√xxEN ISO14184-1

Only free formaldehydex√xLGR-TEGEWAISO 27587

Automotivexx√VDA 275

Formaldehyde specificxx√DIN 53315-BISO 17226-1

Not formaldehyde specificxx√ xDIN 53315-AISO 17226-2

RemarkTextileChemicalsLeatherFormerlyMethod

TEST METHODS IN LEATHER INDUSTRY

Automotivexx√ISO-DIS 17226-3

√xxJapan LAW 112

√xxEN ISO14184-2

√xxEN ISO14184-1

Only free formaldehydex√xLGR-TEGEWAISO 27587

Automotivexx√VDA 275

Formaldehyde specificxx√DIN 53315-BISO 17226-1

Not formaldehyde specificxx√ xDIN 53315-AISO 17226-2

RemarkTextileChemicalsLeatherFormerlyMethod

TEST METHODS IN LEATHER INDUSTRY

FORMALDEHYDE IN LEATHER CHEMICALS

OH OH

SO3H

O

NH2

NH2

O

H H

OH

OHOH

SO3Na

NH

O

NH

NH

O

NH

OH

SO3Na

OH

NH

O

NH

OH

SO3H

OH

SO3Na

NH

O

NH

OH

Fenol

H2SO4

Ureum FormalineUrea Formalin

Phenoltypical phenol syntan

FORMALDEHYDE IN LEATHER CHEMICALS

• Biocides

• Syntans

• Amino resins

• Fatliquors *• Dyeing auxiliaries

• Finishing products

N N

N NH2

NH2

NH2 O

NH2

NH2

O

H H

NH

N N

N NH2

NH

NH

N N

N NH

NH2

NH

OHN

N N

N NH

NH2

NH

NH

O

N N

N NH

NH

NH2

N N

N NH

NH

N NH

O

NH2

N

N N

N NH

N

NH

N N

N NH

NH

NH NH

O

Na3OS

NH

O

NH

SO3Na

SO3Na

SO3Na

NH

O

NH2

Na3OS

Na3OS

Melamine

Formaline UreumUreaFormalin

Melamine

typical melamine resin

• The weakest chemical bonds are made with nitrogen

• Urea

• Melamine

• DCD

• Amino groups of collagen (leather)

CHEMICAL BONDS

APPLICATION OF LEATHER CHEMICALS

CrustFormaldehyde

free resinFormaldehyde

based resinWetblue

Formaldehyde contentRetanning with (no other chemicals used)Formaldehyde content

350 ppmX20 ppmA

250 ppmXX20 ppmC

< 10 ppmX20 ppmB

100 ppmX150 ppmD

0 ppmX0 ppmEtheoretical

• Fillers (not resin based)

• ‘Low’ free formaldehyde products

• So-called formaldehyde free products

• Formaldehyde scavengers

PRODUCT CONFUSION IN THE LEATHER MARKET

DCD based products:

• pronounced filling effect in looser structured areas

• improved fullness/roundness

• improved tightness in the belly and shoulder area

DCD and melamine based retanning agents

Melamine based products:

• filling effect all over the hide

• improved fullness/roundness/softness

• Improved evenness of milling pattern

With three newly developed products you will create

an added value for your customers and for the final end

end user of the shoes, couch or car seat:

• Consistently safer leathers due to innovative chemical technologies

• Free of RSL (restricted substance list) chemicals

• Free of formaldehyde (free and releasable)

• Less rejections of leathers or final luxury articles

ADDED VALUE FOR YOUR CUSTOMERS AND THEIR CLIENTS

• The newly developed DCD - product will not contribute to any formaldehyde release from leather. Besides this, other advantages are:

• Improved fullness/roundness of hides and skins

• Improved filling of loosely structured areas all over the hide

• Improved tightness of hides and skins

• Improved softness of hides and skins

• Improved evenness of milling pattern on furniture upholstery

• Improved evenness of pebble pattern on furniture upholstery

DCD product | ADVANTAGES

SELECTIVE FOR DIFFERENT AREAS OF THE HIDE

DCD product

• The DCD and the melamine based

product both are designed to be

selective for different regions of the

hide. The darker shades indicate the

degree of effectiveness.

• Due to the chemical composition of the

DCD – product it is selectively absorbed

by the more empty structured areas of

the hide. As a result the main amount

applied will be fixed and bound in the

bellies and shoulders, although the

remainder of the hide benefits as well.

• The newly developed melamine based product will not contribute to any formaldehyde release from leather. Besides this, other advantages are:

• Improved tightness of hides and skins

• Improved fullness/roundness of hides and skins

• Improved filling of loosely structured areas all over the hide

• Improved softness of hides and skins

• Improved evenness of milling pattern on furniture upholstery

• Improved evenness of pebble pattern on furniture upholstery

Melamine product | ADVANTAGES

SELECTIVE FOR DIFFERENT AREAS OF THE HIDE

Melamine product

• The DCD and the melamine based

product both are designed to be

selective for different regions of the

hide. The darker shades indicate the

degree of effectiveness.

• The melamine based product is

selectively absorbed by the looser

structures of the hide. As a result the

main amount will be fixed and bound in

the areas that need tightening, although

the remainder of the hide benefits as

well.

SELECTIVE FOR DIFFERENT AREAS OF THE HIDE

COMBINATION

DCD- and melamine based product

• The combination of the two results is a

full coverage of the hide. The amounts

used during the application can be

balanced depending on the raw

material.

• The DCD and the melamine based

product both are designed to be

selective for different regions of the

hide. The darker shades indicate the

degree of effectiveness.

• The third product in this range is a bio-based sustainable product that will not contribute to any formaldehyde release from leather. Besides this, other advantages are:

• Contributes to a cleaner environment and less tannery pollution• Results in leather with significantly improved tightness• Results in leather with improved fullness• Results in leather with a fine, flat grain• Will not contribute to any formaldehyde release from leather• Is free of chemicals that are listed on restricted substance lists

Bio-based syntan | ADVANTAGES

Bio-based syntan | WORKING CLEANER AND SAFER

The bio – based syntan is a completely readily biodegradable

sustainable retanning agent that is free of RSL chemicals (Restricted

Substance List) such as formaldehyde. This enables you to work cleaner

and safer without negative effects on the quality of your leather.

Bio-based syntan | ‘CHEMICAL’ BACKGROUND

It is based on bio-polymers that are sustainable and made from biological materials which can be grown season after season.

When the used bio-polymers are compared to the traditional amino resins there are big environmental advantages. This as the bio-polymers are able to lower carbon emissions and reduce carbon dioxide quantities in the atmosphere. The crops grown for this application reabsorb the carbon dioxide which means that this results in a carbon footprint close to zero.

Next to this it is at least 70% sustainable while common amino resins only have a score of 0 – 2%. The remaining part (30%) of the product consists of >99% biological material.

Bio-based syntan | BIO-BASED COMPONENTS

Bio-based products

are commercial or industrial products (other than food or feed) that are composed, as a whole or for a significant part, of biological products or renewable domestic agricultural (including plant, animal, and marine) or forestry materials. Bio-polymers are often the basis for this type of products.

Bio-polymers

are polymers produced by living organisms or by synthesising. Peptides, proteins, starch, cellulose, DNA and RNA are all examples of bio-polymers.

Bio-based syntan | BIO-BASED COMPONENTS

Leather, Feed, Food / Pharma

FORMALDEHYDE AND LEATHER

Smit & Zoon

The Netherlands

Thank you for your attention.