Sustainable UV-curable low refractive index resins with novel

polymers for polymer cladding materials

Hiroki Tokoro*, Takako Ishikawa, Nobuyuki Koike, Yohzoh Yamashina
DIC Corporation, 12 Yawatakaigan-dori, Ichihara, Chiba JAPAN 290-8585

ABSTRACT

Low refractive index polymers are used as cladding materials for high numerical aperture (NA) fibers. Since transparent
fluoro polymers are ideal for this application, they have been used over many years. However, some fluoro chemicals
face an issue related to perfluoro octanoic acid (PFOA) which is caused by its longtime persistence in the environment
and human body. In this research, non-PFOA type UV curable fluoro resins suitable for cladding were developed with
novel materials. The cured films showed high transparency, good adhesion to glass and low refractive index of 1.359 and
1.386 at 850 nm. Optical fibers prepared with those cladding showed almost equivalent attenuation to a fiber with
commercially available material.
Keywords: High NA, plastic clad silica fiber, polymer, low refractive index, UV cure, fluoro resin

1. INTRODUCTION
High NA fibers are interesting for power transmission, remote sensing or for laser fibers with high pump efficiency.
Especially, plastic clad silica core fibers are widely used in medical, industrial, scientific and military fields. For those
fibers, fluoro polymers with low refractive index and high transparency are used for cladding1-5.
However, United States Environmental Protection Agency has been concerned perfluorooctanoic acid “PFOA” and its
related materials for a decade. PFOA well known as “C8” is very persistent in the environment, so once PFOA is
released to the environment, it can hardly get into biodegradation process. Furthermore, PFOA tends to remain in human
body for long period of time, probably in the scale of years. In 2006, EPA and major companies in fluorochemical
industry launched “the 2010/15 PFOA Stewardship Program”, in which companies committed to reduce global facility
emissions and product content of PFOA and related chemicals by 95% by 2010, and to work toward eliminating
emissions and product content by 20156.
In this study, we developed novel “non-PFOA” type fluoro polymers and the low refractive index coatings. Also
evaluation results of the coatings, cured films, and optical fibers coated by the newly developed coatings as cladding are
reported.

Figure 1. Structure of PFOA

*hiroki-tokoro@ma.dic.co.jp; phone +81-436-41-4367; fax +81-436-43-7482; http://www.dic-global.com/en/

Organic Photonic Materials and Devices XVI, edited by Christopher E. Tabor, François Kajzar,
Toshikuni Kaino, Yasuhiro Koike, Proc. of SPIE Vol. 8983, 89831O · © 2014 SPIE
CCC code: 0277-786X/14/$18 · doi: 10.1117/12.2040913

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 2. METHODOLOGY
Instruments used for this research are shown in Table 1. Cured films (76μm and 1mm thick) were made on glass
substrate using GS Yuasa 160W/cm metal halide lamp under nitrogen atmosphere.

Table 1. Measurement items and instruments

Measurement items Company Model Conditions

Refractive index ATAGO Abbe refractometer Temperature: 25 °C
DR-M2 Wavelength (nm): 486, 589,
656, 850
Viscosity TOKI SANGYO BII Viscometer Temperature: 25 °C
Transmittance HITACHI U4100 UV-Visible-NIR
Spectrophotometer
Elongation A&D TENSILON RTC Temperature: 23 °C
Young’s modulus
Adhesion
TGA SII TG/DTA 6200 rt to 500 °C, 10 °C/min

3. RESULTS AND DISCUSSION

3.1 Synthesis of fluoro polymers
The formulated fluoro coatings consisted of fluoro polymers, monomers, photoinitiators and additives. The four fluoro
polymers were synthesized with non-PFOA type fluoro (meth)acrylates and other monomers as shown in Table 2.
Polymerization was monitored by viscosity. Polymer 1 was designed for lower refractive index, while each formulation
of Polymer 2 and 3 was more focused on higher modulus with different monomers from those of polymer 1. Since some
fiber drawing processes require higher viscosity coatings, Polymer 4 consisted of the same monomer component as
Polymer 2 but had higher viscosity. All polymer solutions were colorless and transparent.

Table 2. Properties of synthesized fluoro polymers

Polymer Fluorine content (wt%) Refractive index (nD25) Viscosity (mPa·s)

Polymer 1 57 1.347 3,050
Polymer 2 54 1.355 3,250
Polymer 3 54 1.354 3,230
Polymer 4 54 1.355 8,000

3.2 Formulation of low refractive index coatings

Solvent free formulation was designed with Polymer 1 to 4, respectively. Basically F1 was designed so as to have
refractive index of 1.38 as cured film at 589 nm of wavelength and the other formulations were for around 1.40.
Refractive index of cured films was obtained as a function of wavelength (Figure 2). The cured films of F1 showed
refractive index of 1.359 and NA of 0.51 (to silica), while both F2 and F3 showed 1.386 and 0.43 at 850nm, respectively.

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 Table 3. Properties of formulations with fluoro polymers

Formulation Containing polymer Refractive index (nD25) Viscosity (mPa·s)

F1 Polymer 1 1.355 2,000
F2 Polymer 2 1.378 2,000
F3 Polymer 3 1.377 2,000
F4 Polymer 4 1.377 4,000

1.44

1.42 1
ái A
1.40
4
ai
> F1
1 C
FL7
,_- 1.38
a,
cc F3
1.36

1.34
400 500 600 700 800 900
Wavelength (nm)

Figure 2. Refractive index of cured films

3.3 Polymer clad fibers using F1, F2 and F3 as cladding

To evaluate the coatings F1 to F3 as cladding materials, multicomponent glass fibers were drawn and it was coated by
claddings according to the formulation of F1 to F3 as well as a reference material generally used. The core / cladding
thickness was 220 / 240 μm. Transmission loss was measured by cut back method (Figure 3). In a range of 800 to 1600
nm, F3 and the benchmark material showed same loss.

--F2
- -F 3
- Standard

0.0
""- µ '.. *arëi#'r"á.i?
800 1000 1200 14ßß 1600
Wavelength (nm)

Figure 3. Light transmission of the polymer clad fibers using F1 to F3

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 3.4 Cured films
Transmittance through the cured films of F2, F3 and F4 with thickness of 1mm was measured as shown in Figure 4. All
samples showed excellent transparency in the visible light region. The data exhibited around 5% loss induced by
reflection at the interface of the surface / air at both side of the cured samples. Comparison of the cured films of F3 and
F4, with the identical monomer composition, showed that the viscosity could be adjusted for fiber drawing conditions
without affecting transparency and refractive index.

00
N
o
co
pittance ( %T)
m
0

',,, 40
C
- F4
,L

20

0
400 700 1000 1300 1600 1900 2200
Wavelength (nm)

Figure 4. Transmittance of cured films of F2 to F4

3.5 Mechanical properties

Mechanical properties of the cured films are shown in Table 4. Preparation of the films was carried out by using
160W/cm metal halide lamp with UV dose of 20kJ/m2 under nitrogen atmosphere and the measured film thickness was
76 μm. Since F1 showed very low refractive index and low modulus, it can be used as primary coating with harder
secondary coatings. Modulus and hardness of F3 was successfully improved by modifying the formulation of F2 (Table
4). Comparison of F3 and F4 suggested that coating viscosity did not affect mechanical properties as in transmittance test.

Table 4. Mechanical properties of cured samples

Formulation Refractive Index Elongation Young’s modulus Shore D

at 850nm (%) (MPa) Hardness
F1 1.359 79.1 1.3 12
F2 1.386 18.0 236 64
F3 1.386 20.0 243 66
F4 1.386 21.0 232 66

3.6 Thermal properties

Thermal degradation behavior of F1 to F3 is shown in Figure 5 and Table 6. All the samples showed 1% or less weight
loss at 200 °C. Especially in the formulation of F1 and F2, decomposition began at around 300 °C, it seems to have
enough durability required for thermal treatment of fibers, for example medical sterilization7.

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 -1_00
0 100 200 300 400 500

Temperature (SC)
Figure 5. TG curve of the cured films
Table 5. Weight loss (%) from TG analysis

Formulation 200 °C 300 °C 400 °C 500 °C

F1 -0.5 -1.3 -82.2 -99.1
F2 -0.9 -1.9 -71.8 -98.9
F3 -0.7 -7.2 -73.6 -98.1

3.7 Adhesion to glass

Adhesion to glass is the important requirement for the fiber claddings, adhesion promoter such as silane coupling agent
is generally used. Adhesion of coatings F1 to F3 to glass was measured with tensilone meter as shown Figure 6.
F1 showed excellent adhesion to glass without the promoter as shown Figure 8, the reason being considered its low
modulus and elastic deformation.

0.20

0.15

N
E
\
Z
á 0.10

0.05

0.00
F1 F2 F3
Figure 6. Adhesion of F1 to F3 to glass substrate

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 4. CONCLUSION
“Non-PFOA” type low refractive fluoro resins are developed for cladding of plastic clad fiber. The resins showed high
transparency and low refractive index as 1.359 and 1.386 at 850nm. Thus these resins can be used for medical fibers and
fiber lasers.

REFERENCES

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