Feipur Feiplar 2014 · Feipur Feiplar 2014 . ... Unique polymer design by own polymerization Kaneka’s polymer synthesis technology enables the best design for sealant and adhesive

Kaneka North America LLC


Feipur Feiplar 2014


Three plants in Europe, Japan, and US continue producing high quality products to supply the world leading sealant companies.

Advantage of MS POLYMER

Four technical centers in Shanghai, Europe, Japan, and US are supporting customer’s development. A new center will start in Kuala-Lumpur this autumn.

Global network


MS POLYMER Global Network

KANEKA MS POLYMERTM

KANEKA INDIA

office KANEKA

MALAYSIA T/S center

KANEKA BELGIUM Production T/S center KANEKA

NORTH AMERICA Production T/S center KANEKA

JAPAN Production T/S center

KANEKA SHANGHAI

T/S center

KANEKA KOREA

office

KANEKA SOUTH AMERICA

Office


O CHCH2O

CH3

Si(OCH3)2

CH3

(CH3O)2Si

CH3

n

Good chemical stability without catalyst

* Low viscosity

* Good compatibility with various additives (SP value = 8 – 9)

A wide variety of formulations providing a broad based platform to address coating, adhesives, and sealant needs

Coatings, Construction, General Industry, Automotive etc.

A Wide Variety of Applications

MS Chemical Structure and Characteristics


CH3 CH3 CH3 CH3

| | | |

(CH3O)2Si-(CH2)3-O-(-CH-CH2-O-)n-(CH2)3-Si(OCH3)2 = R-Si(OCH3)2

CH3 CH3 CH3

| +cat | H2O |

R-Si-OCH3 + H2O -----------------> R-Si-OH ------------------------> R-Si-OH [Step 1: HYDROLYSIS]

| -CH3OH | -CH3OH |

OCH3 OCH3 OH

-CH3OH + R’-Si(OH)2 (CH3) -H2O

+cat

CH3 CH3

| |

R-Si-O-Si-R’ [Step 2: CONDENSATION]

| |

OH OH

The residual Si-OH groups can then further condense with other Si-OH or Si-OCH3 groups to form a

3D network.

Curing Mechanism of MS PolymersTM


• Single most important aspect in the blending processes is to

dry the components (and/or the final formulation)

– MS Polymers + water = stable

– MS Polymers + catalyst = stable

BUT

– MS Polymers + catalyst + water = rapid polymerization

(hydrolysis + condensation)

MS PolymerTM Blending Regimes


MS Polymer -Application Technology

One Component:

Typical MS curing chemistry

One Component w/booster

Faster curing 1K MS

Two Component

Equally divided ingredients into 2 parts

Part A contains catalyst, part B contains water|

Two component MS/Epoxy

Part A MS

Part B epoxy


Typical MS Adhesive/Sealant Formulation

Catalyst

Filler Thixitrope

Stabilizer Pigment

Dehydrator Adhesion Promotors

Plasticizer

MS Polymer

O CHCH2O

CH3

Si(OCH3)2

CH3

(CH3O)2Si

CH3

n


Type of Additive Recommended

Examples Key Functions

Plasticizers Phthalates, PPG

Rheological control;

Viscosity reducer

Modulus reducer; Tg

suppressor

Fillers Talc; Fumed Silica

Calcium Carbonate Provides ‘body’;

Reinforces formulation

UV and light

stabilizers Hindered phenols

Anti oxidants, HALS

Enhances photo-

oxidation

resistance

Provides weathering

resistance; Improves

service life.

Catalysts U220H (Sn(IV)) Accelerates cure

Moisture Scavengers Vinyl silanes Provides storage

stability

Adhesion Promoters Amino/epoxysilanes Promotes adhesion to a

range of substrates

Pigment TiO2; Carbon Black Colorant; Modulus

enhancer

Thixitrope agents Polyamide waxes Allows extrusion

Typical Ingredients and Effect


Formulation

Component Grade NF-1105

MS Polymer S203H 30

S303H 70

Plasticizer DIDP 90

Calcium carbonate Ultra Pflex 160

Q3T 54

Titanium Dioxide Ti-Pure R902 20

Thixotropic agent Disparlon #6500 2

Antioxidant Tinuvin 327 1

UV absorber Tinuvin 770 1

Dehydration agent A-171 3

Adhesion promoter A-1120 3

Hardening catalyst U-220 2

Total 436

General Adhesive/Sealant Product Properties (NF-1105)

Viscosity 1 rpm 1900

by rheometer 2 rpm Pa·s 1100

10 rpm 320

Tack free time min 22

Curability in depth after 1day 3.5

after 3days mm 5.9

after 7days 8.7

Hardness Shore A - 29

Tensile strength M100 MPa 0.52

by dumbbell shape TB 1.5

23°Cx7days EB % 630

Adhesion in peel by hand

non-primer CF

23°Cx7days CF

CFAnodized

Aluminum

Glass

UPC


MS BENEFITS Durability

MS based products have superior durability, excellent weather resistance and

high elasticity.

Adhesion

MS based products show good adhesion without primer on various substrates.

Including PVC, EPDM, Glass, Wood, Stone, and others.

Paintability

MS based products can be painted with various kinds of paints within specified

application windows

Non-stone staining

MS based products has excellent non-staining characteristics against stones, tiles,

plates.

Quick cure

MS based products cure quickly even at low temperatures due to self producing

moisture in curing mechanism.

Easy handling

MS based products viscosity is stable over a wide range of temperatures. Its extrudability is

excellent even at cold temperature.

Non-isocyanate

MS based products are isocyanate free; ensuring an environmentally and worker

friendly product.

Solvent Free

MS products are solvent free meeting the rigorous standards of California and

other environmentally conscious states and provinces. As well as near zero voc

levels.


MS BENEFITS-Weather Resistance

0 152 226 492 859 1,201 1,856

Initial 40 80 160 240 320 480

0 1.5 2.3 4.9 8.6 12.0 18.6

Period (days)

Irradiation (Lannqley x103)

Corresponding years in Japan

MS

PU


Dimension of Sliced Specimens

～ Sampling Sealant ～

　　SURFACE　　SLICE 2 SLICE 1

　　SLICE ０

　　　BACK SIDEDEPTH FROM SURFACE

SIZE OF TEST SPECIMENS10mm x 45mm x 1mm


Mechanical Properties with Different Depth

～ 10 years old 1 part MS sealant ～

Fig. Tensile Test Results of MS-1 Sealant after 10 Years

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

0 1 2 3 4 5 6 7

Depth from Surface (mm)

Te

nsile

Str

en

gth

at 1

00

%

Elo

ng

atio

n (

MP

a)

an

d

Te

nsile

Str

en

gth

at B

rea

k (

MP

a)

0%

100%

200%

300%

400%

500%

600%

700%

Elo

ngation a

t B

reak (

%)

EB

TB

M100

MS-1

after 10 years

Surface


MS BENEFITS- Cold Weather Application


MS BENEFITS- Cold Weather Application


Adhesion on Various Substrates


MS sealant

Silicone sealant

Paintability on Cured Sealant Water based paint


Migration Staining Dirt Streaking Hydrophobic Staining

MS Construction formulation

Non-staining SR

Normal SR

MS Non-staining formulation

Less

Non

Non

NG

Non

Non

???

NG NG

NG

Non

Non

Types of Stone Staining


Mechanism of Dirt Streaking


MS SR SR* PS PU

Granite (Out door exposure for 6 years)

PS MS SR SR*

Artificial Marble (Out door exposure for 4 years)

Remarks; SR* : One Part Type Others : Two part Type

Outdoor Staining Test


Multiple Applications

Sealants and Adhesives


Multiple Applications Industrial



Coatings



Weather Barriers



Spray apply



Panel bonding & flooring


Demonstrating good paintability

Multiple Applications Sealant (paint)


Good for sealing different types of substrate

Multiple Applications Sealant (different substrate)



Marin use


• MS strong points are resistance to movements,

paintability, low risk of staining, weatherability,

universal sealant and easy handling

expansion and connection joints in the building industry.

sealing of joints in prefabricated buildings.

movement joints in high rise constructions.

sealing between window- and doorframes.

exposed movement joints on all usual building substrates

Conclusion: Construction


• MS strong points are primerless adhesion,

solvent and isocyanate free, paintability,

high hardness, early grab.

structural bonding which require elasticity

and high strength

structural bonding in vibrating constructions

elastic bonding of panels

supple bonding in carbodies, caravans and

containers, ship and boat building

Conclusion: Industry



40 years history with widespread application in the world

Long term storage stability Excellent adhesion Low viscosity

Proven and trusted brand



Many types of grades to prepare soft to rigid products

For each practical application, no limitation to mix each other

Various properties with easy production process


KANEKA MS POLYMERTM

- CH2 – CH – O -

CH3

–

( )n - Si OCH3 CH3OSi -

Unique polymer design by own polymerization Kaneka’s polymer synthesis technology enables the best design for sealant and adhesive.

No urethane bond MS POLYMER is non solvent and low viscosity, and does not contain urethane bond. Heat resistance and durability issues by degradation of urethane bond can never happen.


SiPU (Silyl terminated polyurethane)

- Si OCH3 CH3OSi -

Most of “silane modified polymers” are silane terminated polyurethane structures, which are modifications of polyurethane technology. Therefore they have similar disadvantages to PU, such as heat resistance and durability.

Silane coupling agent

Urethane Commercial

PPG Urethane Urethane Commercial

PPG

Silane coupling agent


The reactive silane group of most of SiPU polymers is an unstable type, which causes stability issue. Especially with water, viscosity increase and gelation issue can occur. Also this type of silane causes high modulus and low elongation.

Catalyst for silane can accelerate degradation of urethane bond. Since SiPU has been in the market for only a short time, the impact of long time usage is unknown.

SiPU (Silyl terminated polyurethane)


Viscosity of commercial SiPU polymers

23C MS POLYMER SiPU

S303H S203H S327 SAT010 SiPU1 SiPU2 SiPU3

Viscosity

（Pa･s） 13 3 24 0.6 60 80 50

Based on Kaneka formulation 1105

MS SiPU

S303H SiPU1 SiPU2 SiPU3

Before test

10rpm（Pa･s） 450 680 840 1060

50C 4weeks later

10rpm（Pa･s） 600 〉1200 〉1200 〉1200

Storage stability of commercial SiPU polymers


Mechanical properties of commercial SiPU polymers

100% Modulus（MPa）

Elo

ng

ati

on

(%

)

One of advantages of MS sealant is toughness . Most of SiPU polymers contain trimethoxysilane, which show high

modulus and low elongation . In combination with aminosilane, the trend can be accelerated.

SiPU SiPU


Impact of aminesilane

OCH3

Si

CH3

OCH3O

OCH3

OCH3

Si OCH3N

H

O

O

O C H 3

O C H 3

Si O C H 3

H2N << =

Silane at MS Silane at SiPU Aminosilane

Reactivity of silane reaction

Reaction of aminosilane give a big impact to adhesive performance. In MS formulation, aminosilane can show excellent performance such as better adhesive property compared to the other similar technology as well as good storage stability.

Since reactivity of silane at SiPU is similar to one of aminosilane, it might be difficult aminosilane can transfer to substrates. Also storage stability issue can happen.


Hand peel test Based on Kaneka formulation 1105

MS POLYMER

SPUR

S303H SiPU1 SiPU2 SiPU3

After 23C 7 days curing

Aluminum CF CF CF CF

Stainless CF CF CF CF

Glass CF CF CF CF

PVC CF AF AF AF

After 50C 7 days under

water

Aluminum CF AF CF CF

Stainless CF CF CF AF

Glass CF AF AF AF

PVC CF AF AF AF

Adhesive property of commercial SiPU polymers


Commercial sealant MS SPUR

MS1 SiPU1 SiPU2 SiPU3

Before test

100% Modulus (MPa) 0.62 1.2 0.75 0.89

Tensile strength (MPa) 1.5 1.6 1.4 1.6

Elongation (%) 380 180 260 290

After 80C

2 months

100% Modulus (MPa) 0.77 1.3 0.55 0.76


Elongation (%) 280 130 180 190

After 90C

2 months

100% Modulus (MPa) 0.84 - 0.39 0.82


Elongation (%) 250 90 151 310

Heat stability of commercial SiPU sealants


Decomposition of PU bond may occur

Heat stability of commercial SiPU sealants

SiPU1

SiPU2

SiPU3


MS (Modified

Silicone)

SR (Silicone)

PU (Polyurethane)

SPUR (Silyl-terminated

Polyurethane)

Durability (movement) Good Excellent Good - Mid Good - Mid

UV resistance Good Excellent Good - Mid Good

Adhesion property Excellent - good Excellent - good Good - Mid Good

Heat resistance Good Excellent Middle Good - Mid

Staining Good Poor Good Good

Surface pollution Middle Poor Middle Good - Mid

Paint ability Good Poor Good Good

Cost Good - Mid Good Good Good - Mid

Environmental Friendliness Good Middle （oxime) Middle Good - Mid

General properties in various Sealant

MS has a good balance property, no poor property but no special (excellent) property

MS can be used for a lot of application by formulation technology (Technical service)


Cross-linking of Acryl-Modified MS / SAT (MA)

monomer

• Tg

• Mw

• Functional group

CHCH2O Si(OCH3)2O(CH3O)2Si

CH3 CH3CH3

n

CH2-C CH2-C

R1

R3

Si(OCH3)x(CH3)3-x

R1

C

O

O

R2

Acryl MA/SAT

Si O Si

CH3O

CH3

SiH3C O Si

CH3

Si

CH3

O Si

CH3 AcrylPPO

Acryl

Acryl

PPO

Si

CH3

O

Hybrid

Compatible

(Transparent)


Blushing around joint of sidig-board

※KNK＃１０５formulation

200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600

500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000 6500

ＭＳ

ＭＡ

ＭＳ

ＭＡ

Time(hour) until blushing on thin layer part(150μm) :SWM

Time(hour) until cracks on surface (3mm) : SWM

hv/H2O/heat

Thick Layer Thin Layer

Chalking

Stabilizer hv/H2O/heat Stabilizer

Filler etc.

High Wetherability Sealants


Acryl-Modified SAT for Adhesive

High Strength

Universal Adhesion

High Tack Adhesion

Tensile Shear Strength

Ａｌ ABS PC FRP Melami

ne ＡｃｒｙｌＰＣｌ

7.3 0.8 3.4 3.9 4.2 1.7 2.7

ＳＡＴ２００ Normal MS

CF AF

CF10

AF90

CF70

AF30 CF AF AF

7.8 3.1 6.6 6.4 5.4 3.8 6.1

ＭＡ４４０ Acryl modified

CF

CF10

AF90 CF

CF90

AF10 CF

CF40

AF60 CF

KNK JK-199 Formulation CF: Cohesion Failure, AF: Adhesive Failure


SAT Polymer

Hardening catalyst for Epoxy

Compatibilizer (aminosilane)

Epoxy resin

Hardening catalyst for SAT

A-part

B-part

Compatible (Transparent)

Hardening

Phase separation (Opaque) Tough elastomer

Cured Epoxy particle

(+/- 0.05 – 0.5 mm)

EPX

To introduce high cohesive elements

Solubility control SAT

Design of SAT / EPX system (for high strength)

TEM

Cured STPE

phase

Documents

Feipur Feiplar 2014 · Feipur Feiplar 2014 . ... Unique polymer design by own polymerization Kaneka’s polymer synthesis technology enables the best design for sealant and adhesive