Surface Modification of Chemically Stable Polymeric Materials which Enables

the Solvent Bonding and the Ink-jet Printing using Water-based Ink
H. Kanazawa, A. Inada and Y. Yamaguchi
Department of Industrial Systems, Faculty of Symbiotic Systems Science,
Fukushima University, 1 Kanayagawa, Fukushima 960-1296, Japan
kana@sss.fukushima-u.ac.jp
1

Introduction

Polyolefins such as polypropylene (PP), polyethylene

(PE) or ultra-high molecular weight polyethylene
(UHMWPE) and poly(methyl pentene) (PMP), etc. have
both high tensile strength and resistance to chemical reagents. However, these materials cannot be bonded to each
other or other materials with usual adhesives. Many techniques were examined to improve the adhesive property,[1,2] but, the modified surface property was changed
with time.
We tried to improve the adhesive property of polyolefin
materials by old techniques, but a durable modification
was not obtained. Thus, we tried to combine two or three
methods, and found that the combination of an activation
process by one of old techniques and a chemical treatment
with monomer or polymers was effective for the modification of many kinds of chemical stable polymeric materials.[3,4] This method is named as KANA-USA method.
We further improved this technology, and the modification
of polyolefins, polycarbonate (PC), silicone resins, fluorocarbon resins and engineering plastics such as polyacetal
(POM), polybutylene terephthalate (PBT), polyamides,
polysulfone (PS), polyimide (PI), fluorocarbon resin, polyetheretherketone (PEEK), etc. and several FRPs were examined. The technique was useful for the improvement in
the adhesive property of engineering plastics. Furthermore,
the solvent bonding of modified silicone rubber tubes and
PMP or PP tubes were examined and a good result was
obtained. In addition, a printing by ink-jet printers using
water-based ink on modified materials was examined.

Experimental

2.1 Materials
Polymeric materials of films, sheets, fibers, boards,
rods and tubes were used after washing in methanol.
Commercial hydrophilic monomers, polymers and reagents were used after a simple purification.

2.2 Treatment
The present method is composed of two processes, an
activation process and a chemical reaction process. It is
named as KANA-USA method. First, polymeric materials
were activated by old oxidation methods or energy irradia-

tion processes such as UV, plasma, high-voltage electric

discharge treatment. The activated polymeric materials
were subsequently treated by a chemical treatment process
using solutions of polymers, monomers or other chemical
reagents in the presence of catalysts.

2.3 Measurements
2.3.1 Adhesive polyvinylpyrrolidone (PVP), starch, a
woodwork bond (polyvinylacetate (PVAC)-water mixture :
Konishi Co. Jp), cyanoacrylate adhesive (CA; Aron alpha:
Toa Gosei Kagaku Co.), epoxy resin adhesive (Quick 5 ;
mixture of epoxy resin and polythiol, Konishi Co. Ltd.), a
cyanoacrylate-primer set (Cemedine PPX; primer : organic
amine 1% and heptane 99%; Cemedine Co. Ltd.), etc. were
used.
2.3.2 Adhesion strength a tensile shear bond strength test
and a T peel test were carried out using a Shimadzu
AGS-H5KN.
2.3.3 IR spectra polymeric materials were observed by a
Shimadzu IRPrestige-21 equipped with a Smiths DuraSampl IR II (ATR accessory).
2.3.4 Paints Commercial water-based paints (Asahipen,
Co. Ltd., Japan) which contain synthetic resins (acrylic,
silicone and fluorocarbon resins), pigments and organic
solvents, and water-based urethane car-use paints were
used.
2.3.5 Solvent bonding Modified polymeric material tubes
were coated with normal organic solvents, and they were
connected to each other, and the tubes were laid for several
minutes, and the solvent bonding was finished.
2.3.6 Printing An inkjet printing of modified materials
was carried out by a commercial ink-jet printer with water-based ink.

3 Results and Discussion

3.1 Mechanism
The mechanism of the present process was considered as
given in Scheme 1, by referring the former study. [5] Oxidized polymers (PE-OOH or PP-OOH) formed in the activation process are reacted with reactive compounds (P-X).
The product PP-OR is formed.

and PEEK sheets or boards were modified by the present

method, and bonded to aluminum boards using Quick 5
(epoxy resin and polythiol mixture) and the tensile shear
bond strength test was carried out. The cohesive failure
was observed in all specimens.

3.3 Coating with Water-Based Paints

Polymeric materials modified by the present technique
were coated well with water-based paints. Modified PP
boards were coated with a water-based paint (for car use)
and dipped in water at 40C for 20 days. Subsequently, the
cross-cut test was carried out. The PP boards gave a
full-mark, 100/100 in the cross-cut test. These requirements are available for the car use.
Silicone rubber sheets cannot be coated with a water-based paint. Corona-discharged silicon rubber sheets
have to be coated with water-based paints immediately
after the treatment; we confirmed that the coating was impossible 5 hours after the corona discharge treatment. On
the other hand, the silicone rubber sheets treated by our
method gave good coating property even five years after
the processing.

3.4 Solvent bonding

PP, silicone rubber and PMT tubes modified by the present method were bonded to each other by the solvent
bonding. Figure 1 gives a PMT-made T-tube connected to
a silicone rubber tube by the solvent bonding. The silicone
rubber tube (right side) could not be pulled out from the T
tube in the tensile strength test. It is impossible to bond a
silicone rubber tube to the left side which is not modified.
This technique is suitable for the production of medical
devices.

Scheme 1

3.2 Improvement in adhesive property using

adhesives
The adhesive property of polymeric materials using adhesives was improved well by the present method. Modified PP boards could be bonded to other materials with
usual adhesives, and the material fracture was observed in
the tensile shear bond strength test of specimens.
The modified silicone rubber sheets got wet in water and
were bonded to wooden boards using a PVAC adhesive
(woodwork bond).
Modified PC boards were bonded to paper with starch or
PVA glues. Fluorocarbon resins (PTFE, PFA, PVDF), PI

Fig.1 PMT-made T-tube connected to a

silicone tube by the solvent bonding

3.5 Ink-jet printing

Polymer films (PP, PE, PET, PC, silicone resin, etc.)
were modified by the present method, and a
post-processing suitable for the inkjet printing with water-based ink was investigated. Figures 2, 3 and 4 give the
results for PP, PET films and silicone rubber sheets. Un-

treated materials were not printed by the ink-jet printer

with water-based ink. It is preferable to make a coating on
the printed materials with transparent coating materials in
order to protect the surface.

Fig.2 Modified PP (lower) and untreated PP

(upper) films printed by an ink-jet printer with a
water-based resin ink (Dainichi Seila Co. Ltd.)

Fig.4 Modified silicone rubber (lower) and

untreated PP (upper) sheets printed by an
ink-jet printer with a water-based resin ink
(Dainichi Seika Co. Ltd)

Conclusions

The present method gave the improvement in the adhesion, painting and printing properties of chemically stable
polymeric materials. The modified property is durable as
compared with usual corona or plasma discharges.The
modified polymeric materials are useful in many fields and
for preparing new FRP.

Reference

Fig.3 Modified PET film printed by an

ink-jet printer, Epson PX-105 with a water-based resin ink.

1. R.H. Young, Sr., et. al., United State Patent,

No.5432000 (1995).
2. M. Kinoshita, Japanese Patent Application,
No.09012752 (1997).
3. H. Kanazawa, USA Patents No.7294673 and No.
6830782B2.
4. H. Kanazawa, Japanese Patent No.4229421, etc.
5. T. Matsui, A. Yamaoka, and Y. Yamaguchi, Nippon
Kagaku Kaishi, 732 (1992).