Three Bond Technical News
Issued January 1, 199748

New Materials for On-Line-Gasket System(OLGS)
Introduction ________________________________________________
Since the company's founding, Three Bond has developed and supplied a variety of sealants,
including liquid gaskets, to prevent leaks in industrial products. For almost 20 years, our products havebeen used in assembly lines operating throughout Japan. During these years, silicon materials havecome into wide use in transportation-related equipment and devices such as engines, transmissions,and differential gears, contributing significantly to cost reductions and the streamlining of assembly
processes.
This issue of Three Bond Technical News introduces a two-part fluorine-based liquid gasket and ananaerobic-curing liquid gasket -- both newly developed for Three Bond's On-Line-Gasket System(OLGS) -- and explains their technical characteristics.

Contents
Introduction
I. Two-part fluorine-based liquid gasket.............................................................. 2
II. Anaerobic-curing liquid gasket ........................................................................ 6

1

I.

Two-part fluorine-based liquidgasket (Three Bond 1119)

1.

Development background

Fluorocarbon rubber is now seen as an essential
industrial material due to its outstanding properties
and characteristics, such as its high resistance toheat, chemicals, and solvents.
Demand for fluorocarbon rubber in Japan is said
to total 1,600 to 1,700 tons in volume, withapproximately 60% of this demand attributable toautomotive applications. This points to thesuitability of fluorocarbon rubber for the various
requirements of today's automobile industry -- interms of safety, environmental friendliness, energy
conservation, and comfort. Automotive applicationsof fluorocarbon rubber can be divided roughly into
two groups: those involving fuel systems and those
involving engine lubrication systems. Specifically,
fluorocarbon rubber is used as a sealing agent inengine parts, fuel hoses, and diaphragms, and also
as a vibration insulator in engine mounts. Becauseof its superb properties, fluorocarbon rubber is used
in applications of increasingly harsh conditions
demanding higher performance -- automotive
applications in particular. In addition, demands forlower cost are emerging, as are those for higher
functionality in order to satisfy various regulations.
Fluorocarbon rubber manufacturers are working
hard to develop higher-quality, better-grade
materials to respond to these developing needs.
In an attempt to respond to such expectations,Three Bond has now developed a completely new
two-part fluorine based liquid gasket, a room
temperature curing product that are different fromconventional molded products such as O-rings,
sheets, and hoses.

2.

Product outline

One-part RTV silicon rubber hardens from thesurface as the polymer-terminus hydrolytic group(≡Si-OR) reacts with moisture in the air andchanges to a silanol group; the rubber thenundergoes condensation reactions as the silanolgroup comes into contact with other hydrolytic
groups. Even if the main polymer component is
replaced with perfluoropolyether, curing begins
from the surface according to the same reactions
seen in RTV silicon, as shown in Fig. 1. However,measurement of the moisture permeability of thehardened layer indicates that perfluoropolyether has

2

a much lower moisture permeability value thansilicon, as shown in Table 1; thus,
perfluoropolyether prevents the penetration ofmoisture into deeper layers, and only a thinsuperficial layer hardens.

Perfluoropolyether polymer unit

Fig. 1

Reaction mechanism of one-part
RTV fluorocarbon rubber

Table 1 Problem of moisture permeability
Moisture permeability (1 mm in thickness) g/m2•24h

Silicon100

Perfluoropolyether

4

Deep curing

×

Agent A Agent B

Main polymer
Amine

Ketimine

KetoneDeep curing
Quick curing

Water

Fig. 2 Improvement of deep curing performance
To address the problem of moisture permeability
seen with fluorocarbon rubber (as shown in Table 1),
the two-part fluorine-based liquid gasket developedby Three Bond incorporates a reaction mechanism(see Fig. 2) to cause internal water generation at thetime two liquids are mixed, thus allowing thesurface to harden in the same way as in one-part
RTV and also enabling uniform curing at the depth
below surface.
Thus, Three Bond 1119 is room temperature
curing two-part fluorine based liquid gasket andfluorocarbon rubber can be formed in a short periodof time when agent A and agent B are mixed at aratio of 1 to 1.

3.

Features

Bond 1119 (Table 2), characteristics in the cured(1) Excellent resistance against chemicals(2) Excellent resistance against heat(3) Excellent low-temperature characteristics(4) Non-combustibility, water repellency,
oil-repellency, low moisture permeability(5) Hardens into elastic rubber in a short time atroom temperaturestate (Table 3), chemical resistance characteristics(Table 4), heat resistance characteristics (Table 5),
fuel-C resistance characteristics (Table 6), engine
oil resistance characteristics (Table 7), and low
temperature characteristics (Table 8).

The following shows physical properties of Three
Table 2 Physical properties
Three Bond 1119

Measurement

Item

Test method

Unit

Agent A

Agent B

Appearance

3TS-201-02-

Black paste

White paste
260 (2600)

Viscosity

3TS-210-03

Pa•s (P)

150 (1500)

Specific gravity

3TS-213-02

-

1.76

Workable time-

Minutes10

Viscosity after mixing*1Pa•s (P)190 (1900)

1.80*1 Measurement of viscosity after mixing: Fill 100-ml polyethylene with Three Bond 1119 mixed using a dedicated dispensing
system, and start measurement immediately using 3TS-210-03 device. The value measured after 10 minutes is determined as"viscosity after mixing."

Table 3 Characteristics in cured state
Test method

Unit

Measurement

Hardness (JIS-A)

Item

3TS-215-01-

39

Elongation rate

3TS-320-01

%

97
2

1.03 (10.5)

Tensile strength

3TS-320-01

Mpa (kgf/cm )Shearing adhesive strength (Fe/Fe)

3TS-301-23

Mpa (kgf/cm )20.54 (5.5) CF100

Shearing adhesive strength (Al/Al)

3TS-301-23

Mpa (kgf/cm )20.59 (6.0) CF100

Curing condition: 25°C × 7 days

CF: Coagulation factor

Table 4 Chemical resistance characteristics
Test method

Immersion temperature

Unit

Characteristic value

Gasoline (unleaded)

Test item

JIS K 6820

45 to 50°C

wt%

-3

Kerosene

JIS K 6820

45 to 50°C

wt%

-2

30% Sulfuric acid

JIS K 6820

25°C

wt%

-2

10% Hydrochloric acid

JIS K 6820

25°C

wt%

-2

10% Caustic soda

JIS K 6820

25°C

wt%

-2

TolueneJIS K 6820

25°C

wt%

-2

Methyl ethylketone

JIS K 6820

25°C

wt%

-2

Methanol

JIS K 6820

25°C

wt%

-2
24-hour immersion

3

Table 5 Heat Resistance
Unit

120°C × 240 hrs.

120°C × 500 hrs.

Hardness (JIS-A)

-

57

60

Elongation rate

%

Item

70

61

2

2.53 (25.8)

2.52 (25.7)

Tensile strength

Mpa (kgf/cm )Shearing adhesive strength (Fe/Fe)

Mpa (kgf/cm )21.38 (14.1) CF50

1.61 (16.4) CF100

21.57 (16.0) CF50

1.73 (17.7) CF100

Shearing adhesive strength (Al/Al)

Mpa (kgf/cm )Table 6 Fuel-C resistance characteristics
Unit

25°C × 240 hrs.

25°C × 500 hrs.

Hardness (JIS-A)

-

39

42

Elongation rate

%

86

87

Tensile strength

Mpa (kgf/cm )2

1.14 (11.6)

1.41 (14.4)

2

Mpa (kgf/cm )0.50 (5.1)

0.35 (3.6)

2

0.62 (6.3)

0.53 (5.4)

Item

Shearing adhesive strength (Fe/Fe)
Shearing adhesive strength (Al/Al)

Mpa (kgf/cm )Table 7 Engine oil resistance characteristics
Unit

150°C × 240 hrs.

150°C × 500 hrs.

Hardness (JIS-A)

-

51

52

Elongation rate

%

Item

Tensile strength
Shearing adhesive strength (Fe/Fe)
Shearing adhesive strength (Al/Al)

85

84

2

Mpa (kgf/cm )2.74 (28.0)

2.47 (25.2)

2

Mpa (kgf/cm )0.92 (9.4)

0.81 (8.3)

20.84 (8.6)

0.98 (10.0)

Mpa (kgf/cm )Engine oil: Grade 5W-30SH

Table 8 Low-temperature characteristics
Unit-30°C × 240 hrs.

-30°C × 500 hrs.

Hardness (JIS-A)

-

42

40

Elongation rate

%

Item

Tensile strength
Shearing adhesive strength (Fe/Fe)
Shearing adhesive strength (Al/Al)

4

90

108

2

Mpa (kgf/cm )1.13 (11.5)

1.28 (13.1)

2

Mpa (kgf/cm )0.74 (7.5)

0.69 (7.0)

20.76 (7.8)

0.76 (7.8)

Mpa (kgf/cm )4.

Main applications

In automobile production, Three Bond 1119 isused as a sealant for engine parts. It can be used as asealant for lubricating devices such as oil pumps
and oil filters; fuel devices such as fuel tanks, fuelpipes, fuel pumps, fuel filters, and charcoal
canisters; fuel injection devices such as sensors; andintake devices such as intake manifolds and surge
tanks.
In the chemical industry, the product can be used
as a sealant for pumps and piping for chemicals, or
as a lining or coating agent for tanks that requirechemical resistance.
The product can also be used in office equipment,
including parts and components requiring heat
resistant rubber in photocopiers.
The product can also find applications in theenergy industry, nuclear power industry, andaerospace industry.

5.

Key points of development

Perfluoroelastomers presently available on themarket are copolymers with tetrafluoroethylene
(TFE)
and
perfluoromethyl
vinyl
ether
CF3OCF=CF2 (φ-MVE) as the main monomers,
combined with a small amount of special
crosslinked monomers as a third component. The
backbone chains of perfluoroelastomers based on
TFE/φ-MVE are completely fluorinated; they thus
offer excellent resistance to chemicals, solvents, andheat. However, their relatively rigid backbone
chains make such perfluoroelastomers difficult toprocess; nor is crosslink processing easy. In
addition, these polymers are very expensive. As aresult, they are generally sold on the market as
molded products.
By constructing a backbone chain with a flexible
perfluoropolyether polymer, Three Bond has
succeeded in developing an innovative new
product: "liquefied fluorocarbon rubber," or Three
Bond 1119. In other words, by synthesizing a bothend functional perfluoroelastomer and incorporating
the crosslink technology used in one-part RTV
silicon, we have achieved room-temperature curing.
Further, by resolving the issue of moisturepermeability discussed above, we have also enabled
thick layer curing.

6.

Future topics

There is room for improvement in the rubber
based properties of Three Bond 1119. Since theproduct employs one-part RTV silicon crosslink
technology in the crosslink group, the heat
resistance of the perfluoroelastomer itself is not
maximized. Further improvements are possible
through the application of advanced polymer
physico-chemical engineering techniques. However,current technology in the chemical field does notallow us to take such an approach. This represents
the main topic to be addressed in the future.
Needless to say, when it becomes possible tosynthesize perfluoroethers for use as raw materials,
at low cost, and when it is possible to mold and curethe material easily, perfluoroelastomers will be able
to replace certain other elastomers, generating
significant market demand in the process. In fact,
no currently available elastomer can offer
performance superior to that of perfluoroelastomer
in terms of the harsh environmental conditions seenin the space industry and semiconductor field. The
future of perfluoroelastomers is thus bright, witheven higher performance anticipated.
参考文献の訳が抜けています。

5

II.

Anaerobic-curing liquid gasket

It has been more than 30 years sinceanaerobic-curing liquid gaskets first becamecommercially available. An anaerobic curing liquidgasket does not harden under normal opened air
conditions after application. The polymerizing cureprocess occurs rapidly immediately after thematerial is formed into a thin layer between metalparts at a joint or fitting where oxygen is absent.
Because this characteristic leads to improved
workability on production lines, anaerobic-curingliquid gaskets have been used as Formed-In-Place
Gaskets (FIPG), mainly in the automobile andconstruction equipment manufacturing industories.
This issue introduces a new member to of Three
Bond's anaerobic-curing liquid gasket lineup, andexplains its technical characteristics.

to the large clearances involved, RTV silicon does
harden in such cases, as it is moisture-curing.
Finally, efficient application technology is now
available, involving the use of a Mohno pump.
Anaerobic-curing liquid gaskets are generally
used on flat groove-less flanges made of rigid
die-cast aluminum offering a uniform contact
surface with no clearance or warpage. However, as
parts materials are becoming lighter in order toreduce product weight, demand is growing for new
anaerobic-curing liquid gaskets, such as those madeof RTV silicon, that are flexible enough to follow
the movement of joints. To respond to such
emerging needs, Three Bond has introduced a new
product developed by adding flexibility to thefeatures of the conventional anaerobic-curing liquidgasket. The company has also resolved the previous
drawback relating to heat resistance, and has
improved the dispenser application technology.

1.

2.

Introduction

Background

It is well known that this type of anaerobic-curingcomposition is comprised of a radical polymericmonomer with acrylate and/or methacrylate as themain constituent, as well as a polymerization
initiator, curing accelerator, polymerization
inhibitor, and other elements.
Factors that have promoted the widespread use ofanaerobic-curing liquid gaskets in the automobileand construction machinery industries include thefollowing.
(1) Prevents loosening of bolts otherwise seen due to theeffect of material fatigue common to solid gaskets(2) Eliminates the need to provide clearances inequipment design(3) Offers high adhesive strength for improved rigidity at
joints and connections(4) Excess sections extending from joints/connections
after assembly disperse into oil(5) Surface finishing process has minimal effect onadhesive and sealing performance(6) Does not harden until assembly is completed(7) Excellent resistance to chemicals(8) Does not cause foaming in oil

RTV silicon is the main FIPG material used inJapan today. The reasons for its popularity include
its excellent heat resistance and low-temperature
characteristics.
Additionally,
althoughanaerobic-curing liquid gaskets do not harden
quickly when used on pressed steel flanges (such as
oil pans and automatic transmission fluid pans) due

6

Three Bond 1131F and 1133B

2-1. Outline
Three Bond developed the 1131F and 1133B
anaerobic-curing liquid gasket products that are
exclusively used on metal flanges. The Three Bond
1131F offers excellent flexibility, similar to that of
RTV silicon, at the same time offering improved
connection rigidity. Three Bond 1133B is flexible
and offers high adhesive strength and heat
resistance. The dedicated bead application system
also incorporates dramatically improved coating
technology.
2-2. Physical properties and characteristics
Three Bond 1131F
External appearance
Viscosity
Thixotropic ratio
Specific gravity
Set time
Shearing adhesive strength (Al)Elongation
Tensile strengthBlue paste
50 Pa•s (500P)
3.1
1.12
5 min
2
3.9 Mpa (40kgf/cm )150%
2
5.3 Mpa (54kgf/cm )Three Bond 1133B
External appearance
Viscosity
Thixotropic ratio
Specific gravity
Set time
Shearing adhesive strength (Al)Elongation
Tensile strengthBlue paste
100 Pa•s (500P)
2.9
1.12
5 min
2
6.1 Mpa (62kgf/cm )100%
2
18.6 Mpa (190kgf/cm )Curing time (hours)* Aluminum shearing adhesive strength* Test piece: Aluminum A2024P* Clearance: 0.02 mm

Fig. 1 Relationship between temperature and curing speed

Relative strength (%)

Features of Three Bond 1131F and
1133B
1) Flexibility: The use of urethane-modified
polyester and urethane-modified polyether as
the backbone chain of the base polymer(oligomer) has led to unprecedented levels of
flexibility as well as of rigidity.
2) Resistance against chemicals: Due to the greatermolecular weight of the cured material,
resistance against engine oil, automatictransmission fluid, gear oil, etc. is very high.
3) Curing speed: Although conventional products
require a long setting time under
low-temperature conditions (5°C), the additionof a new curing catalyst has reduced the setting
time significantly.
4) Adhesive strength: Since Three Bond 1131F wasdeveloped with an emphasis on flexibility,
adhesive strength was set to a medium level.
With Three Bond 1133B, flexibility is slightly
lower, but adhesive strength is higher.
5) Minimum foaming: Because the base polymer isurethane-modified acrylate, the products will not
foam after being dispersed in oil.
6) Dispersibility in oil: Because urethane-modified
acrylate is used as the base polymer, theproducts offer high mutual solubility in various
types of oil; uncured substances disperse in oil.
7) Maintainability: Since the base polymer isurethane-modified acrylate, spraying the Three
Bond PANDO 391D gasket remover swells thistype of liquid gasket left on flange surface, thus
allowing easy removal with a scraper.

Relative strength (%)

2-3.

Curing time (hours)* Aluminum shearing adhesive strength* Test piece: Aluminum A2024P* Temperature: Room temperature

Fig. 2 Relationship between clearance and curing speed
Sheet steel

Relative strength (%)

Aluminum

2-4. Characteristics(1) Temperature and curing speed (Fig. 1)
Anaerobic-curing liquid gaskets reach practicalstrength (50% of final strength) inapproximately one hour with an ambient
temperature above 5°C.
(2) Clearance and curing speed (Fig. 2)
Because anaerobic-curing liquid gaskets havepolymerization inhibition function against
oxygen in radical polymerization, curingperformance decreases if the clearance is large.
If the clearance is less than 0.1 mm, there will
be no problems in practical application.

Aluminum

Curing time (hours)* Shearing adhesive strength* Clearance: 0.02 mm* Temperature: Room temperature

Fig. 3 Relationship between material and curing speed

7Material
ADC

Cu

Si

Fe

4.0 to 10.0 9.6 to 12.0 1.0 or lessAI
Remnant

A2024P

3.8 to 5.0 0.5 or less 0.5 or less

Remnant

A1050P

0.05 or less 0.25 or less99.5 or more

0.4 or lessRelative strength (%)(3) Material and curing speed (Fig. 3)
Metal surfaces affect the curing performance ofanaerobic-curing liquid gaskets. Since ordinary
die-cast aluminum (ADC) contains copper, it is highactive material. For this reason, aluminum A2024P
test pieces, which have components similar to thoseof die-cast aluminum, were used in the basic
property test.
Table 1 Components in test piece materials(Wt%)

Ambient temperature (°C)

Relative strength (%)

Fig. 5 Thermal shearing adhesive strength

Immersion time (hours)* Test piece: Aluminum A2024P* Clearance: 0.02 mm* Temperature: Room temperature

Fig. 6 Shearing adhesive strength of TB 1131F after
immersion in automatic transmission fluid

Immersion time (hours)
Surface roughness* Test piece: Aluminum A1050P* Clearance: 0.02 mm* Temperature: Room temperature

Fig. 4 Surface roughness and tensile adhesive strength8* Aluminum shearing adhesive strength* Test piece: Aluminum A2024P* Clearance: 0.02 mm

Relative strength (%)

Tensile adhesive strength (MPa)(4) Surface roughness and adhesive strength (Fig. 4)
Finishing precision has almost no effect onadhesive strength.
(For (1), (2), (3), and (4), Three Bond 1131F and
1133B exhibit similar tendencies.)(5) Thermal strength (Fig. 5)
Since the cured material softens under hightemperatures, the resin strength decreases. As aresult, the adhesive strength tends to decrease as
well. Nonetheless, Three Bond 1133B retains
sufficient adhesive strength at temperatures above
120°C.
The following shows the results of various
reliability tests.
(6) Three Bond 1131F and 1133B's resistance toautomatic transmission fluid (Figs. 6 and 7)(7) Shearing adhesive strength of Three Bond
1131F and 1133B after thermal aging (Figs. 8
and 9)(8) Shearing adhesive strength after cold-heatcycles (Fig. 10)* Test piece: Aluminum A2024P* Clearance: 0.02 mm* Temperature: Room temperature

Fig. 7 Shearing adhesive strength of TB 1133B after
immersion in automatic transmission fluidRelative strength (%)

Relative strength (%)
Leaving time (hours)* Test piece: Aluminum A2024P* Clearance: 0.02 mm* Temperature: Room temperature

Fig. 8 Shearing adhesive strength of TB 1131F
after thermal aging* Test piece: Aluminum A2024P* Clearance: 0.02 mm* Temperature: Room temperature

Fig. 9 Shearing adhesive strength of TB 1133B
after thermal aging

Bead coating system foranaerobic-curing liquid gasket

3-1. Outline
This bead coating system is a precision machinethat coats anaerobic-curing liquid gasket in a thinbead on a flange surface.
3-2. Features(1) No discontinuity of bead
The system has mechanisms to allow coatingwith removing air bubbles in the material.
(2) Detection device to check discontinuity
The system certainly finds discontinuity withhigher level of image processing thanconventional methods.
3-3. Mechanism(1) Air bubble removal (Photo 1) (Fig. 11)
A screw with pitch decreasing continually toward
the tip (in the direction of the nozzle) creates acontinuous volumetric change of threads andcompresses the anaerobic-curing liquid gasket whiletransporting the material. Air bubbles escape to alower-pressure area and are released to theatmosphere from the rear end of the screw. Thismechanism separates air bubbles from the material,
thus preventing bead discontinuity during
dispensing material from the nozzle tip.

Relative strength (%)

3.

Leaving time (hours)

Number of cycles* Aluminum shearing adhesive strength* Test piece: Aluminum A2024P* Clearance: 0.02 mm* Cycle condition: -30°C × 1 hr. to +150°C × 1 hr. per cycle* Temperature: Room temperature

Fig. 10 Shearing adhesive strength after cold-heat cycles

Photo 1

9

Screw pump and cartridge unit

Quick exhaust
valve

Air
chamber

DC motor
Plunger

Controller unit

Sample chamber

Approx.410
Air vent hole

Cartridge (tank)
Capacity: 170 cc

Continuous/intermittent
switchAir gauge

Timer set switch

Reversetimer cap
Warning
lamp

Timer
Compression
screw

Grease nipple

NozzleRegulator

Power switch
Speed control dialFig. 11 Anaerobic-curing liquid gasket precision application system(2) Application detection (Photo 2)
An image processing system with a CCD camera
is used to detect discontinuity, width, and positional
deviation of coated beads. To prevent influences ofintensity changes in ambient light and diffusedreflections, contrast image processing system isused for accurate verification. Various conditions
such as gap width, deviation amount, and minimum
bead width can be set precisely, and teaching
operations are performed almost automatically.
3-4. Equipment
By combining the outstanding mechanisms
described above and the coating technology(including robotics) that has cultivated through thedevelopment of the OLGS, the equipment performs
high-precision
bead-form
coatingofanaerobic-curing liquid gaskets. Three Bond also
manufactures and supplies coating systems which
satisfy specific customer needs. For more details of
the systems, contact Three Bond Engineering Co.,Ltd.
Satoshi Hosoki
Hiroyuki Ouchi
Transport Equipment Business Development
Section, Development Department

10

Photo 21456 Hazama-cho, Hachioji-shi, Tokyo 193-8533, Japan
Tel: 81-426-61-1333