Note: Descriptions are shown in the official language in which they were submitted.
WO 93/21248 1 2 1 1 ~ 4 ~ 1 PCI/US93/02037 .
LIQUID CUR~BLE RESIN COMPOSITION
F; el d nf th~ Tnvention
The present invention relates to a liquid curable resin
composition which has superior curing characteristics,
durability, and the like, adheres well to various types of
substrates, and is therefore useful as a coating material for
plastics, wood, porcelain, glass, paper, and the like, and as
an optical molding material, three-dimensional molding
material, printing plate material, and the like. :~
.`:
0 Descrl~t~ on of the Prior Art
Generally, an optical fiber is provided with a re~in
coating comprising a flexible primary coating layer on the `.
8urface of the optical fiber, with the object of protecting
and reinforcing the bare optical fiber threads immediately ~
15 after hot melt spinn~ng of the glas~ fiber, the outside of ~:
which is covered in turn by a secondary coating layer. The
coating material used to form these coatings must have the -`
following characteristics:
(1) be a:liquid at room temperature and have high
~: 20 process~ability;
(2) pro~ide good productivity at a high curing rate;
(3) show superior flexi~ility;
(4) exhibit very little physical change during a wide range
of temperature changes ; ~:
(5) have superior thermal resistance and superior resistance
to hydrolysis;
(6) show superior long term reliability with little physical
chan~es over time;
(7), show superior resistance to chemicals such as acids and
alkalis;
18) exhibit low moisture and water absorption; and
- 19) exhibit superior light resistance.
To meet these requiremen~s various liquid coating
; materials of the radiation curable type have been de~eloped. :~
. .
W093/212~ 2 1 ~ ~ 'I 2 1 PCT/US93/02037
They are compositions containing urethane acrylate using, for
example, tetrahydrofuranethylene oxide ring opening
copolymers (Japanese patent Laid-open (ko-kai) No.
86450/1986), tetrahydrofuranpropylene oxide ring opening
copolymer (Japanese Patent Laid-open (ko-kai) No.
181170/1985), or tetrahydrofuranalkyltetrahydrOfuran
copol~mers (Japanese ~atent Laid-open (ko-kai) No.
115964/1989).
Compositions in which these polyether copolymers are
used have drawbacks still to be solved. That is, urethane
acrylates using these polyether copolymers are insufficient
in one or more of the characteristics, including resistance
to ultraviolet light, heat resistance, light resistance
(resistance against changing its color into yellow under
light radiation~, heat resistance (resistance against
changing its color into yellow when heated), and flexibility.
Accordingly, an ob~ect of the present invention is to
provide, with due considexation to the drawbacks of such
conventional compositions, a ~iquid curable resin composition
ideal as a covering material for optical fiber, which has a
low viscosity at room t~mperature and exhi~its good
processability when used to coYer optical fibers, has good
optical curing characteristics r can accommodate high speed
optical fiber production, and in the cured state shows
excellent flexibility, good resistance to heat~ ultraviolet
light, and oil, and exhibits suitable adherence to optical
fiber.
This object is achieved in the presen~ inven~_on by the
! provision of a liquid curable resin composition comprising a
urethane (meth)acrylate obtained by the reaction of:
(A) a polyether polyol compound containing, as a
structural units, ~roups represented by the following
formulae (1), ~2), and (3),
(1) -CH2CH20-
WO93/212~ 2 1 1 ~ ~ 2 1 PCT/US93/02037
(2) -CH2CH(R)O-, and
(3) one or more groups selected from groups (a),
(b), and (c) below,
-CH2CH2CI 12CH20- (a)
R
C--~ (b) ~
Rl :
,.
{~1~~ (c)
wherein R represents an alkyl group containing two or more
carbon atoms, and R1 and R2 are independently se~ected $rom a
hydrogen atom or ~ methyl group; :~
(B) a polyisocyanate compound; and
(C3 a ~meth~acrylate compound having a hydroxy group.
The liquid cur2ble resin compQsition of the present invention
has an extxemely low Young's modulus at roo~ tempexature,
shows a suitable adher.ing strength to glass fiber, has
super~or durability, exhibits high speed curing performance,
and is thus suitable as a coating material for optical fiber.
~m~
A polyether polyol compound (here~nafter referred to as
polyol compound ~A)) used in the present invention must
contain structural uni~s of th~ above formulae (1), (2), and
t3). There are ~o limitations as to the manner in which
WO~3/212~ ~ 2 1 PCT/US93/02037
these structural units are polymerized. They may be
polymerized by random, block, or graft polymerization.
Such a polyol compound (A) can be prepared by the ring-
opening polymerization of ethylene oxide, l,2-alkylene oxides
with 4 or more carbon atoms, e.g, 1,2-butylene oxide, l,2-
hexene oxide, or the iike, and one or more compounds selected ~;
from polytetramethylene glycol, bisphenol A, and bisphenol F, `~
by a known method.
The proportion of structural unit (1) contained in
polyol compound (A) is 5 to 50% by weight, and preferably 10
to 45%. If the amount of the structural unit ~1) is less
than 5%, improvement in the oil resistance of the composition
after curing is insufficient; if greater than 50%, water
resistance and flexibility of the composition after curing
tend to be.lowered. A preferable proportion of structural
unit ~2) is 10 to 90%, with a particularly preferable range
being 20 to 80%. The proportion of structural unit (3) is
preferably 5 to 85%, and more preferably 10 to 70%.
The num`ber of carbon atoms of R in the unit of formula
(2) conta~ned in ~meth)acrylate (A) is preferably 2 to 12,
with a particularly preferable range being 2 to 4.
The number average molecular weight of the polyol
compound (A) is usually in a range of 200 to 10,0~0, and
preferably S00 to 8,000. If the number average molecular
weight is less than 200~ the Young's modulus of the cured
material at room temperature or at lower temperatures
increases, and there is a tendency toward an increase in
transmission losses from ~ide pressure when it is applied to
optical fiber; if greater than 10, t the viscosity of the
resulting composition tends to increase, resulting in
impaired coa~ing performance of the composition when it is
coated onto the optical fiber.
The polyol compound (A) may contain any structural units
other than the above structural units of the formulae ~1) to
~3), to the extent that the effects of the present invention
are not affected, so long as polyol compound (A) contains all
.
WO93J21248 2 1 1 ~ '1 2 I PCT/US93/02037
` 5
of these 3 structural units. Examples of such other
structural units include -CH2CH2CH20-, -CH2CH(CH3)O-, and the :;
like.
In addition, polyols which do not have the above
S structural units (l), (2) and (33 can be used in combination.
Examples of such polyols include polyether polyols, polyester
polyols, polycarbonate polyols, polycapralactone polyols, and
other polyols.
Examples of polyether polyols which do not ha~e the
above structural units (l), (2~ and (3~ include, for example,
polyethylene glycolO l,2-polypropylene glycol, l,3- :
polypropylene glycol, l,2-polybutylene glycol, `
polyisobutylene glycol, propylene oxide-te~rahydrofuran
copolymers, methyl tetrahydrofuran-tetrahydrofuran ..
copolymers, and the like.
Examples which can be given of polyester polyols include
polyester polyols obtained by reacting a polyvalent alcohol .
such as ethylene glycol, polyethylene glycol, pxopylene
glycol, polypropylene glycol, tetramethylene glycol,
polytetramethylene glycol, l,6-hexane diol, neopentyl glycol,
l,4-cyclohexanedimethanol, 3-methyl-l,5-pentanediol, l,9-
nonanediol, 2-methyl-lr8-octanediol, or the like with a
polybasic acid such as phthalic acid, isophthalic acid,
terephthalic acid, maleic acid, fumaric acid, adipic acid,
sebacic acid, or the like; and commercial produ ts such as
Kurapol P-2010, PMIPA, PR~-A, P~A-A2, PNA2000 (manufactured
by Xuraray C5. ), and the like.
Examples which can be given of polycarbon~te polyols
include 1,6-hexanepolycarbonate and produ ts available on the
market, such as DN-980, DN-981, DN-982, DN-983 ~manufactured
~y Nihon Polyurethane Co., Ltd.~, PC-8000 (manufactured by
PPG of the US), and the like.
Examples of polycaprolactone polyols include
polycaprolactonediols obtained by reacting ~-caprolactone
with a divalent diol such as ethylene glycol, polyethylene
glycol, propylene glycol, polypropylene glycol,
W093/21248 2 1 1 ~ 1 2 ~ PCT/US93/02037
tetramethylene glycol, polytetramethylene glycol, 1,2-
polybutylene glycol, 1,6-hexanediol, neopentyl ~lycol, 1,4-
butanediol, or the like, as well as PLACCEL-205, 205Ah, 212,
212AL, 220, 220AL (manufactured by Daicel Co.), and the like.
Examples of other polyols include ethylene glycol,
propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-
hexanediol, neopentyl glycol, 1,4~cyclohexanedimethanol,
ethylene oxide and/or propylene oxide-addition diols to
bisphenol-A, ethylene oxide and/or propylene oxide-addition
diols to bisphenol-F, ethylene oxide and/or propylene oxide-
addition diols to hydrogenated bisphenol-Ar ethylene oxide
and/or propylene oxide-addition diols to hydrogenated
bisphenol-F, dimethylol compounds of dicyclopentadiene,
tricyclodecanedimethanol, poly ~-methyl-d-valerolactone
polyol with a terminal hydroxy group, polybutadiene with a
terminal hydroxy group, hydrogenated polybutadiene with a
terminal hydroxy group, castor oil-modified polyols,
polydimethylsiloxane with a diol terminal group,
polydimethylsiloxane carbitol-modified polyols, and the like.
~he number average molecular weight of these polyols is
usually 200 to 10,000, and preferably 500 to 8,000.
Given as examples of polyisocy~nate compound (B) which
can be used in the present invQn~ion are 2,4-tolylene
diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene
diisocyanate, l,4-xylylene diisocyanate, 1,5-naphthalene
diis~cyanate, m-phenylene diisocyanate, p-phenylene
diis~cyanate, 3,3'-dimethyl-4,4'-diphenylmethane
dtisocyanate, 4,4'-diphenylme~hane diisocyanate, 3,3'-
dimethylphenylene diisocyanate, 4,4'-biphenylene
3Q diisocyanate, l,6-hexane diisocyanate, isophorone
diisocyanate, methylenebis(4-cyclohexyl isocyanate), 2,2,4-
tximethylhexamethylene diisocyanate, bis(2~
isocyanateethyl)fumarate, 6-isopropyl-i,3-phenyl
diisocyanate, 2,2-bis(4'-isocyanic acid)propane, lysine
diisocyanate, and the like. Of these particularly preferable
WO93/21248 2 1 1 ~ 4 2 1 PCT/US93/02037
are 2,4-tolylene diisocyanate, isophorone diisocyanate, .-
2,2,4-trimethylhexamethylene diisocyanate, and the like.
Examples of (meth)acrylates with a hydroxyl group,
component (C~ used in the present invention, include 2-
hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-
phenyloxypropyl(meth)acrylate, l,4-butanediol
mono~meth)acrylate, 2-hydroxyalkyl(meth)acryloyl phosphate, -~
4-hydroxycyclohexyl(meth)acrylate, 1,6-hexanediol
monotmeth)acrylate, neopentylglycol mono(meth)acrylate,
tr~methylolpropane di(meth)acrylate, trimethylolethane
di(meth)acrylate, pentaerythritol tri(meth)acrylate,
dipentaerythritol penta(meth)acrylate, (meth)acrylates :
represented by the following formula (4),
CH2--C(Rl)-COOCH2CH2-(0C=OCH2CH2CH2CH2CH2)n~OH (4)
wherein Rl is a hydrogen atom or a methyl group and n is an
integer from 1 to 15, preferably 1 to 4.
In addition, compounds obtained by an addition reaction
between compounds containing a glycidyl group, such as, a}kyl
glycldyl ether, allyl glycidyl ether, glycidyl
(meth)acrylate, or the like, and ~meth)acrylic acid can be
used. Among these, particularly desirable are 2-hydroxyethyl
~meth)acrylate, 2-hydroxypropyl lmeth)acrylate, and the like.
The urethane (meth)acrylates used in the present
in~ention can be prepared by the reaction of the
abovement~oned polyol compound (A), polyisocyanate compound
~B), and ~meth)acrylate compound containing a hydroxy group
~C~; specifically, by reacting the isocyanate group in ~he
polyisocyanate compound ~B) with the hydroxy group of polyol
compound (A) and the hydroxy group of the (meth)acrylate
compound ~C). The reaction can be carried out, for example,
by the following manners.
(1) All of polyol compound (A), polyisocyanate compound
~B), and (meth)acrylate compound containing a hydroxy group
~C) are charged in the reactor for the reaction.
;
wo 93,2l248 2 1 1 ~ ~ ~ I PCT/US93/02037
(2) Polyol compound (A) and polyisocyanate compound ~B)
are first reacted, and then the resulting reaction product is
reacted with (meth)acrylate compound containing a hydroxy
group ~C).
(3) Polyisocyanate c~mpound (B) and (meth)acrylate
compound containing a hydroxy grou~ (C) are first reacted,
and then the resulting reaction product is reacted with
polyol compound (A).
(4) Polyisocyanate compound ~B) and (meth)acrylate
compound containing a hydroxy group (C) are first reacted,
then wi~h polyol compound ~A), and the resulting reaction
product is finally reacted again w~th (meth)acxylate con~pound
containing a hydroxy group (C).
The propsrtions of polyol compound ~A), p~lyisocyanate
15 compound (B), and (meth)acrylate compound containing a -
hydroxy group (C) used for the reaction are such that l.l to .-
3 equivalents of isocyanate groups in polyiso~yanate cQmpound
(B) and O.l to l.5 equi~alents of hydroxy groups in
(meth)acrylate compound containing a hydroxy group (C) are
u8ed for l equivalent of the hydroxy group contained in
polyol compound ~A).
In the reaction of these compounds, O.Ol to l.0 parts by
weight of a urethanization catalyst such as copper
naphthenate, cobalt naphthenate, zinc naphthenate, n-
25 butyltindilaurate, triethylamine, triethylenediamine, 2-
methyltriethylenediamine, or the like, is used usually to lO0
parts by weight of the total reactants used in these
reactions. The reaction temperature is normall~ lO ~o 90C,
and preferably 30 to 8QC.
The amount of urethane (meth)acrylate thus obtained used
in the composition of the present invention is preferably 5
to 93%, but 20 to 87% is considered ideal in maintaining the
coating characteristics when covering the optical fibex wire~
and in maintaining the flexibility and long term reliability
of the coated material after curing.
W O 93/21248 2 1 1 ~ 4 2 1 PC~r/US93/~2037
The molecular weight of urethane (meth)acrylate isusually 700 to 20,000, and preferably 1,000 to 10,000 (number
average molecular weight). `
To the liquid curable composition of the present
invention, radiation curable compounds other than urethane
(meth)acrylates, reaction diluents, and other additives may
optionally be incorporated to the extent that the effects of
the present inventlon are not adversely affected. ~;~
Other radiation curable compounds than the urethane
(meth)acrylates of the present ~nvention such as other
urethane (meth)acrylates, polyester (meth)acrylates, epoxy
~meth)acrylates, polyamide ~meth)acrylates, polysiloxanes
with~~meth)acryloyloxy group, and the like can be
incorporated in the compos~tions of the present in~ention.
They may be. added either singly or two or more may be added
together.
Examples of reaction diluents include monofunctional and
polyfunctional compounds. Specific examples of
monofunctional compounds which can be given include 2- ;~
20 hydroxyethyl tmeth)acrylate, 2-hydroxypropyl ~meth)acrylate, ;.
2-hydroxybutyl lmeth)acrylate, methyl (meth)acrylate, ethyl
(meth~acrylate, propyl ~meth)acrylate, isopropyl
(meth)acrylate, butyl ~meth)acrylate, amyl (meth)acrylate,
isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl
(meth)acrylatel isoamyl (meth)acrylate, hexyl (meth)acrylate,
heptyl ~meth)acrylate, octyl ~meth)acrylate, isooctyl
(meth)acrylate, 2-ethylhexyl (meth~acrylate, nonyl
(meth)acrylate, decyl (meth~acrylate, isodecyl
(meth)acrylate, undecyl ~meth)acrylate, dodecyl
~meth)acrylate, lauryl (meth~acrylate, octadecyl
tmeth)acrylate, stearyl ~meth)acrylate, tetrahydrofurfuryl
(meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene
glycol (meth)acrylate, benzyl ~meth)acrylate, cyclohexyl
(meth)acrylate, phenoxyethyl ~meth)acrylate, polyethylene
glycol mono~meth)acrylate, polypxopylene glycol
mono~meth)acrylate, methoxyethylene glycol (meth)acrylate,
WO93/21248 2 1 1 ~ ~ 2 i PCT/US93/02037
ethoxyethoxyethyl (meth)acrylate, methoxypolyethylene glycol
~meth)acrylate, methoxypolypropylene glycol (meth)acrylate,
dicyclopentadiene (meth)acrylate, dicyclopentanyl
(meth)acrylate, dicyclopentenyl (meth?acrylate,
tricyclodecanyl (meth)acrylate, isobornyl (meth)acrylate,
bornyl (meth)acrylate, d~acetone ~meth)acrylamide,
isobutoxymethyl (meth ) acrylamide, N-vinyl pyrrolidone, N-
vinyl caprolactam, N,N-dimethyl (meth)acrylamide, t-octyl
(meth)acrylamide, dimethylaminoethyl ~meth)acrylate,
diethylaminoethyl (meth)acrylate, 7-amino-3,7~dimethyloctyl
(meth~acrylate, N,N-diethyl (meth)acrylamide, N,N'-
dimethylaminopropyl (meth)acrylamide,
(met~acryloylmorphoxine; vinyl ethers such as hydroxybutyl
vinyl ether, lauryl vinyl ether, cetyl vinyl ethex, 2-
ethylhexyl vinyl et~er, and the like; maleic acid esters,fumaric acid esters, and compounds represented by the
following formulas ~5) to (7~.
CH2=C(R3)-C-o-(R40)m~
O (5)
wherein R3 indicates a hydrogen atom or a methyl group; R4 is
an alkylene group with 2 to 6, preferably 2 to 41 carbon
atoms; R5 is z hydrogen atom or an alkyl group with 1 to 12,
preferably 1 to 9, carbon atoms; and m is an integer from O
25 to 12, preferably from 1 to 8.
I' - I
CH2=C(R3)-C-(o-R6-c)poCH2 ~ ) (6)
O O
W093/2124B PCT/I~S93/02037
Il 211~21
wherein R3 is the same as above, and R6 is an alkylene group
with 2 to 8, preferably 2 to 5, carbon atoms, and p is an
integer from 1 to 8, preferably from 1 to 4.
~7
CH3 o-CH ~7
CH2=CH(R3~l C-(ORj-C3p-o-cH2-cicH ," C~ ~,
CH3 ~ \ (7)
R R ~`
wherein R3, R6, and p are the same as above, R7 is a hydrogen
atom or a methyl gxoup.
Examples of commercial products which can be used are
ARONIX M111, M113, M114, M117 (manufactured by Toa Go~ei
Chemical Co.), KAYARAD TCllOS, R629, R~44 ~manufactured by
Nippon Rayaku Co.) and OISCO~T 3700 (manufactured by Osaka -:~
Organic Chemicals Co.) and the like. :
, Examples of polyfunctional compounds include
15 trimethylolpropane tri~meth)acrylate, pentaerythritol ~:
tri(meth)acrylate, ethylene glycol di(meth)~crylate,
tetraethylene glycol di(me~h)acxylate, polyethylene glycol
di(meth)acxylate, 1,4-butanediol di~meth?acrylate, 1,6- -
hexanediol di(me~h)acrylate, neopentyl ~lycol
di(meth)acrylate, trimethylolpropanetrioxyethyl
~meth)acryla~e, tris(2-hydroxye~hyl)isocyanurate
tri~meth)acrylate, tris~2 hydroxyethyl)isocyanurate
di~meth)acrylate, ~ricyclodecanedimethanol di~me~h)acrylate,
epoxy (meth~acrylates ob~ained by the addition of a
~meth)acrylate to bisphenol A diglycidyl ether, triethylene
glycol divinyl ether, epoxy compounds, cyclic epoxy
compounds, vinyl sulfides, vinyl urethanes, vinyl ureas, and
the like.
W093/21~ 2 1 1 8 ~ 2 ~ PCT/US93/0~037
Examples of commercial products which can be used are
COPIMA- W, SAl002, SA2007 ~manufactured by Mitsubishi
Petrochemical Co.), BISCOAT 700 ~manufactured by Osaka
Organic Chemical Co.), R604, DPCA-20, DPCA-30, DPC.A-60, DPCA-
120, HX-620, D-310, D-330 (manufactured by Nippon Kayaku
Co.), ARONIX M210, M215, M315, M325, (manufactured by Toa
Gosei Chemical Co.), and the like.
An appropriate reaction diluent can be used for a
composition depending on the characteristics to be demanded
of the composition.
When flexibility, especially flexibility at low
temperatures, is required, ~meth)acrylate compounds, of which
the homopolymer have a glass transition temperature of -10C
or below, are preferably used among the above-mentioned
reaction diluents.
Given as-preferable examples of such (meth)acrylate
compounds are commercial products such as A~ONIX ~102, ~111,
M1~3, M114, M117 (manufactured by Toa Gosei Chemical Co.),
RRYARAD TCllOS, R629, R644 (manufactured by Nippon Rayaku
Co.)~ and the like.
When good adhesion and ~uring characteristics are
required, N-~inyl pyrrolidone and N-~inyl caprolactam among
the above-mentioned reaction ~iluents are preferably used.
These reaction diluents can be incorporated in the
25 composition of the present in~Jention preferably in an amount
of 5 to 60%, and particularly preferably lû to 40%. The
composition of.the pre~ent invention is cured by heat and/or :~
radiation Radiation in this case means the application of
infrared, visible light, and ultraviolet rays, as well as
ionized rays such as X-rays, electron rays, a rays, ~-rays,
T-rays, and the l~ke.
When the composition of the present invention is cured
by heat, a radical polymerization initi~tor, for example
peroxides, azo compounds or the like, is generally used.
Specific examples are benzoyl peroxide, t-butyloxybenzoate,
~zobis~sobutyronitrile, and the like.
WO93/21248 2 1 1 ~ '1 2 1 PCr/US93/02037
! 13
!
When the compositi~n of the present invention is cured
by light, a photopolymerization initiator, and, as required,
a photosensitizin~ agent are used. Examples of
photopolymerization initiators include 1-hydroxycyclohexyl
phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone,
fluorenone, benzaldehyde, fluorene, anthraquinone,
triphenylamine, carbazole, 3-methylacetophenone, 4-chloro-
benzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diamino-
benzophenone, Michler's ketone, benzoin propyl ether, benzoin
ethyl ether, benzyldimethylketal, 1-~4-isopropyl-phenol)-2-
hydroxy-2-methylpropane-1-on, 2-hydroxy-2-methyl-1-
phenylpropane-l-on, thioxanthone, diethylthioxanthone, 2-
isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-l4-
(methylthio)phenyll-2-morpholinopropane-1-on, 2,4,6- `~
trimethylbepzoyldiphenylphosphine oxide, and commercial
products such as Irugacure 184, 651, 500, 907, 369, CG24-61
~all manufactured by Ciba Geigy), Lucirine LR8728
~manufactured by OASF), Darocure 1116, 1173 (manufactured by
Merck), Ubecryl-P36 (manufactured by U~0 Co.), and the like.
Exam~les of photosensitization agents are triethylamine,
diethylamin~, N-methyldiethanolamine, ethanolamine, 4-
dimethylaminobenzoic acid, 4-dimethylaminomethyl benzoatet 4-
dimethylaminoethyl benzoate, 4 dimethylaminoisoamyl benzoate,
and commercial products such as Ubecryl-P102, 103, 104, 105
manufactured by the UCB Co., and the like. These
polymerization initiators and photosensitization agents can
be added individually or in mixture~ of two or more. In the
ca-~e where the composition of the present invention is cured
by both heat and ultra~iolet lightr the above-mentioned
radical polymerization initiators can be used in combination.
; The amount of polymer~zation initiator used is
preferably 0.1 to 10% of the composition.
In addition, other additives may optionally be added to
the composition of the present invention. Such additives
include epoxy resins, polyamides, polyamidoim~des,
polyurethanes~ polybutadienes, chloroprene, polyethers,
.
W093/2t2~ 2 ~ 1 8 ~ 2 1 PCT/US93/02037
14
polyesters, pentadiene derivatives, styrene/~utadiene/styrene
block copolymers, styrene/ethylene/butene/styrene block
copolymers, styrene/isoprene/styrene block copolymers,
petroleum resins, xylene resins, ketone resins, fluorine
5 containing oligomers, silicone-type oligomers, polysulfide .
type oligomers, and the like. .
Other types of additives which can be used as required
in addition to those listed above $nclude antioxidants, :
coloring agents, ultraviolet absorbers, photostabilizers,
10 silane coupling agents, heat polymerization inhibitors, -
leveling agents, surfactants, preservatives, plasticizers,
lubricants, solvents, fillers, aging inhibitors, wetting `
agents, coating surface improvers, and the like. Commerc1al .~-
antioxidants which can be used are Irganox l0l0, 1035, 1076, ~:
15 I222 ~manufactured by Ciba Geigy), and the like. Given as -~
examples of commercial absorbers are Tinuvin P234, 320, 326,
327, 328, 213 (manufactured by Ciba Geigy), Sumisorb ll0, .
130, 200 ~Sumitomo Chemical Co.), and the like. Commercial
photo~tab~lizers which can be used include Tinuvin 292, 144, -`
622LD::(manufactured by Ciba Geigy), Sanol LS7 70
- ~(manufactured by Sankyo Chemical Co.), and the like.
Examples of silane coupling agents which can be given are t- ~^
aminopropyltriethoxy silane, t-mercaptopropyltrimethoxy
silane, t-methacryloxypropyltrimethoxy silane, and commercial
products such as SH6062, 6030 (manufactured by Toray Silicone :~
Co.~, XBE903/ 603, 403 (manufactured by Shin-Etsu Chemical
Co.), and the like. :
The liquid curable resi~ composition of the present
invention can be manufactured by mixing the abo~e components
using commonly known methods.
The viscosity of the liquid curable resin composition of
the present invention obtained in this manner is usually 200
to 20,000 cp at 25C, and preferably 2,000 to l0,000 cp at
25C.
: 35 When the composition of the present invention is used as ;~
:~: a~primary coatlng material for optical fiber, the Young's
WO93/2124~ 2 1 18 1 21 Pcr/vss3/o2o37
modulus after curing is 0.05 to 0.5 kg/mm2, and particularly
preferable is C.06 to 0.13 kg/mm2. The Young's modulus of
the cured material at -40 to 60C i5 usually 0.01 to 10
kg/mm2.
:
EXAMPLES
The present invention will now be explained with
reference to the following examples, which ar~ in no way
limiting of the scope of the invention. In the examples
below "parts" means "parts by weight".
Example 1
Preparation of urethane acrylate [A-l~
Into a reaction ve~sel equipped with a stirrer, 170.0 gm
of isophorone diisocyanate, 1 gm of dibutyltindilaurate, and
0.3 gm of 2,6-di-tert-butyl-4-methyl phenol, as a
polymerization inhibitor, were charged. Then, 59.2 gm of
hydroxyethyl acrylate was added to the mixture while
controlling the temperature below 20~C. After the addition,
the mixture was stirxed for 1 hour while maintaining the
temperature at 10 to 20C, followed by the addition of
1,020.8 gm of copolymer diol of ethylene oxide, 1,2-butylene
oxide, and polytetramethylene glycol (1:5:4 by weight) with a
number average molecular weight of 2,000, while controlling
the temperature at 40 to 50C. The mixture was stirred for a
further 5 hours at 50 to 60C to complete the reaction, thus
obtain`ing urethane acrylate [A-1~ with a number a~erage
molecular weight of 4,900.
Example 2
Preparation of urethane acrylate [A-2]
Into a reac~ion vessel equipped with a stirrer, 168.2 gm
of isophorone diisocyanate, 1,044.6 gm of copolymer of
ethylene oxide, 1,2-butylene oxide, and bisphenol A (1:7;1 hy
weight) with a number a~erage molecular weight of 2,0521 and
0.3 gm of 2,6-di-tert-butyl-4-methyl phenol, as a
w0~3/212~ 2 1 1 ~ ll 2 1 PCT/VS93/02037
16
polymerization inhibitor, were charged. After cooling the
mixture to 15C in an ice-cooled bath, 1 gm of
dibutyltindilaurate was added to initiate the reaction at 30
to 40C for 2 hours. After the addition of 47.2 gm of
hydroxyethyl acrylate, the mixture was stirred for 5 hours at
a temperature of 50 to 60C to obtain urethane acrylate [A-2]
with a number average molecular weight of 6,140.
Example 3
Preparation of urethane acrylate [A-3]
Into a reaction vessel equipped with a stirrer, 100 gm
ARONIX M113TM (manufactured by Toa Gosei Chemical Co.), 153.3
gm of isophorone diisocyanate, 1 gm of dibutyltindilaurate,
and 0.3 gm of 2,6-di-tert-butyl-4-methyl phenol, as a
polymerization inhibitor, were charged. Then, 1,056.6 gm of
copolymer diol of ethylene oxide, 1,2-butylene oxide, and
hydrogenated b~sphenol A (47.1 : 41.2 ~ 8 by weight) wi~h
a number average molecular weight of 2,040 was added to the
mixture while controlling the temperature at 40 to 50C.
Afte~ the addition, the mixture was reacted for 2 hours.
40.1 gm of hydroxyethyl acrylate was added and the stirring
was continued for a further 5 hours at 50 to 60C to complete
the reaction, thus obtaining urethane acrylate [A-3~ with a
number average molecular weight of 7,240.
Example 4
Preparation of urethane acrylate lA-4]
Into a reaction vessel equipped with a stirrer, 331.1 gm
of isophorone diisocyana~e, ~ gm of dibutyltindilaurate, and
0.3 gm of 2,6 di~text-butyl-4-methyl phenol, as a
polymerization inhibitor, were charged. Then, 173.0 gm of
hydroxyethyl acrylate was added to the mixture while
controlling the temperature below 20C. After the addition,
the mixture was ~tirred for 1 hour while maintaining the
temperature at 10 to 20C, followed by the addition of 745.8
gm of polytetramethylene glycol with a number average
WO93/21248 17 2 I 1~ 4 ~ ~ PCT/US93/02037
molecular weight of l,000, while controlling the temperature
at 40 to 50C. The mixture was stirred for a further 5 hours
at 50 to ~0C to complete the reaction, thus obtaining
urethane acrylate [A-4] with a number average molecular
weight of l,680.
Example 5
Preparation of comparative urethane acrylate [B-l~
Into a reaction vessel equipped with a stirrer, 170.0 ~m
of isophorone diisocyanate, 1 gm of dibutyltindilaurate, and
0.3 gm of 2,6-di-tert-butyl-4-methy~ phenol, as a
polymerization inhibitor, were charged. Then, 59.2 gm of
hydroxyethyl acrylate was added to the mixture while
controlling the temperature below 20C. After the addition,
the mixture was stirred for l hour while maintaining the
temperature at lO to 20C, followed by the addition of
1~0~0.8 gm of a copolymer diol of tetrahydrofuran and
propylene oxide (3:7 by weight) with a number average
molecular weight of 2,000 (PPTG lOOO,~manufactured by
Hodogaya Chemical Co.) while controlling the temperature at
40 to 50C. The mixture was stirred for a further 5 hours at
50 to 60C to complete the reaction, thus obtaining urethane
acrylate ~B-l] with a number average molecular weight of
4,900.
Example 6
Preparation of comparative urethane acrylate ~B-2 ]
Into a reaction vessel equipped with a stirrer, 130 . 3 gm
of 2, 4-tolylene diisocyanate, 1 gm of d~butyltindilaurate,
and 9.3 gm of 2, 6-di-tert-butyl-4 methyl phenol, as a
polymerization inhibltor~ were charged. To the mixture was
added 1070.0 gm of poly~etramethylene glycol with a number
average molecular weight of 2,000 (PPTG 2000, manuf~ctured by
Hodogaya Chemical Co.) was added while controlling the
temperature at 40 to 50C, followed by the reaction for 2
hours. Then, 49.6 gm of hydroxyethyl acrylate was added and
W093/21~ 1 8 ~ 2 ~ PCT/US93/02037
18
the reaction was continued 5 hours at a temperature of 50 to
60C while stirring, thus obtaining urethane acrylate [B-2]
with a number average molecular weight of 5,840.
Example 7
Into a reaction vessel equipped with a stirrer, 55 parts
of urethane acrylate [A-l], 30 parts of ARONIX Ml13, as a
reaction diluent, 7 parts of Kayarad TCllOS ~a product of
Nippon Kayaku Co.), 5 parts of N-vinyl pyrrolidone, 1.5 parts
of 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, 0.3 part
of Irganox lO35 ~manufactured by Ciba Geigy), O.l part of
Sumisorb llO (manufactured by Sumitomo Chemical Co.), as a
absorber, O.l p~rt of diethylamine, as a photosensi~izing
agent, and l part of silane coupling agent (SH 6062,
manufactured by Toray Silicone Co.) were charged and mixed
with stirring at 50~ to 50C to obtain a transparent liquid
composition with a viscosity of 3,700 cp at 25~C.
Example 8
~Into a reaction vessel equipped with a stirrer, 55 parts
of urethane acrylate [A-2], 25 parts of ARONIX Ml13, 12 parts
of isobornyl acrylate, 5 part~ of N-~inyl caprolactam, l.5
parts of 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, 0.3
part of Irganox 1035 (manufactured by Ciba Geigy), O.l part
of diethylamine, and 1 part of SH 6062 were charged and mixed
with stixring at 50 to 60C to obtain a transparent liquid
composition with a ~iscosity of 3,000 cp at 25~C.
Example 9
Into a reaction ~essel equipped with a stirrer, 60.5
parts of urethane acrylate [A-3~, 37 parts of ARONIX M~13, 5
parts of N-vinyl pyrrolidone, 1.5 parts of 2,4,6-
trimethylbenzoyldiphenylphosphine oxide, 0.3 part of Irganox
1035 (manufactured by Ciba Geigy), O.l part of diethylamine,
and l ~art of SH 6062 were charged and mixed with stirring at
WO93/21248 ~ 2 1 PCT/US93/02~37
19
50 to 60C to obtain a transparent liquid composition with a
viscosity of 5,000 cp at 25C.
Example 10
Into a reaction vessel equipped with a stirrer, 60 parts
of urethane acrylate [A-4], 20 parts of
tricyclodecanedimethanol diacrylate, 10 parts of isobornyl
acrylate, 10 parts of N-vinyl caprolactam, 1.5 parts of
2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 0.3 part
of Irganox 1035 (manufactured by Ciba Geigy) were charged and
mixed with stirring at 50 to 60C to obtain a transparent
liquid composition with a viscosity of 2,000 cp at 25C:.
~ . .
Comparative Example 1
A composition was prepared in the same manner as in
Example 7, except that 55 parts of the urethane acrylate ~B-
1~ was u~ed instead of the urethane acrylate [A-l ] ~ A
transparent liquid composition with a ~iscosity of 3,000 cp
at 25C was obtained.
Comparative Example 2
A composition was prepared in ~he same manner as in
~xample 8, except that 30 parts of the urethane acrylate ~B-
2] was used instead of the urethane acrylate [A-2). A
transparent liquid composition with a viscosity of 11 r 00O cp
a~ 25C was obtained.
Test Examples
1. Film Tests
Test leaves were prepared from compositions obtained in
the above Examples and Comparative Examples and served to the
evaluations according to the following met~ods.
~1) Preparation of test leaves
The liquid compositions were applied to glass plates
using a 150 applicator to obtain cured films by irradiation
WO93/21248 2 ~ 2 1 PCT/VS93/02037
with ultraviolet rays at 25 mJ/cm2 or 500 mJ/cm2. Next, the
cured films were peeled from the glass plates and tempered
for 24 hours at a temperature of 23C and 50% RH, to obtain
the test leaves.
(2) Measurement of Young's modulus (conforming to JIS K7127
Standard)
The Young's modulus of each test leaf was measured in a
tension tester at 23C or -40C at a drawing rate of l mm/min
and a bench line interval of 25 mm.
(3) Gel Proportion
The initial weight (Wo) of the cured film was measured,
then the film was extracted for 12 hours in a Soxhlet
extraction flask using methyl ethyl ketone as a solvent.
After extraction, the film was dried in a vacuum drier
at 50C for 12 hours, then after standing for one hour at
room temperature the final weight (WI~ was measured. The gel
proportion was calculated using the following formula.
Gel proportion = Wl/Wo x lO0 (%)
(4) Weight Change -
The weight of the cured films obtained by irradiation
with ultraviolet light at 500 mJ/cm2 was determined ~initial
weight: Wo). After the heat resistant and light resistant
tests, the films were left for l hour at room temperature to
determine ~ts weight (dry weight: Wl~. The weight change was
calculated according to the following formula.
Weight Change = (Wl-Wo)/Wo x lO0 (%)
(5~ Heat Resistance Te~t
The cured films obtained by irradiation with ultraviolet
light at 500 mJ/cm2 were held in a thermostat at 120~C for 15
days. The Young's modulus and gel proportion of the films
were then measured. The results are shown in Table l.
(6) Light Resistance Test
~ ight resistance tests were performed on the films cured
at 500 mJ/cm2 using a Q W weathering acceleration machine
(manufactured by Q-panel Co.). The lamp used was a UV0-3I3.
After 200 hours in the machine, the outer appearance of the
WO93/21~48 2 1 1 ~ PCT/US93/02037
film was examined and the Young's modulus and gel proportion
were measured. The results are ~hown in Table l.
- TABLE 1
___________________________________________________________
Comparati~e
Examples __ExamDles
Evaluation Item l 2 3 l 2
_________________________ ___ _________________________ ___
t~3C]
Young's modulus (kg/mm2)
25 m/cm2 0.06 0.06 0.06 0.05 0.11
500 m/cm2 0.07 0.06 0.06 0.08 0.18
Gel proportion (%)
25 m/cm2 88 90 88 82 85
S00 m/cm2 89 91 89 88 90
___________________________________________________________
a~e~ eat R~esl ~tant Te~t
500 r~ 2
Young's mo~ulus
25 (kg/mm2) 0.05 0.06 0.05 0~05 0.07 -
Cel Proportion ~)86 - 87 86 82 6S
Color change into
yellow Non Non Non Non Changed
_ _ _ _ _ _ _ _ ._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~ = _ _ _ _ _ _ _ _ _ _ _ _ ._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
500 m/cm2
Gel Proportion (%)84 83 83 50 83
We~ght 5hange -0.3 -O.l -0.2 -lO -l.5
Color change into
yellow Non Non Non Non Changed
____________ ______________________________________________
WO~3/~ 2 1 1 S ~ 2 1 PCT/U593/~2U37
2. Drawing Tests
Using an optical fiber drawing machine, two layers of a
composition, according to the combination in Table 2, was
applied to optical fibers and then cured by irradiation with
ultraviolet rays to obtain coated optical fibers. The mean
diameter of the optical fiber core was 125 ~m, that of the
fiber covered with the primary layer 200 ~m, and that of the
fiber covered with the secondary layer 250 ~m.
The covered optical fibers were prepared at drawing
speeds of 180t 360, and 720 mimin, and subjected to the tests `
according to the following methods. The results are shown ~n
Table 2..
.. ...
(1) Gel Proportion
The initial weight ~Wo) of the coated fibers, cut to a
length of 4 cm, was determined (initial weight: Wo), and the
f~bers were extracted for 12 hours in a Soxhlet extract;ion
flask using methyl ethyl ketone as a solvent.
After extraction, the fibers were dried in a vacuum
drier at 50C for 12 hours, then after-standing for one hour
at r~om temperature the final weight ~dry weight: Wl) was
determined.
Thereafter, the optical fibers were calcined for 30 :
minutes in an electric ~urnace at ~00C to remove the coated
layers and to collect the optical fiber material, of which
the we~ght ~Wf) was determined.
The gel proportion was calculated using the following
formula.
Gel proportion = tWl-Wf)/(Wo-wf) x 100 (%~
3. En~ironment Test
(1) Light Resistance
! Coated optical fibers drawn at 360 m/min were exposed to
fluorescent light (2,000 lux) for 30 days t~ evaluate their
external appearance, and to determine the change in weight
and the a unt of hydrogen gas generated.
,
WO93/21248 2 ~ 1 ~ 'I 2 L
~ PCT/US93/02037
~3
Method of Evaluation
~a) External Appearance
Coated layers, fibers~ and their interface were
mlcroscopically observed to investigate the presence or
absence of vacant spaces, peeled portions, liquid drops, and
foreign materials.
~b) Change in Weight
The change in weight by the exposure to fluorescent
light was determined according to the following formula.
Change in Weight = (Wb-Wa)/(Wa-Wf) x 100 (%)
wherein Wa is the weight of the coated fiber before exposure
to fluorescent light, Wb after the exposure, and WE is the
weight of the optical fiber obtained after removal of covered
material by calcination in the an electric furnace at 700C
for 30 min~tes.
~c) Generation of Hydrogen Gas
The amounts of hydrogen gas before and after the light
resistant test were determined by the following method. The
coated optical fiber was accurately weighed, placed in a vial
wit~ a known weight, and heated at 100C for 4 hours. The air
in the head space of the vial was collected by means of a gas
~ight syringe and the air was introduced to a gas
chromatography to qua~titatively analyze the amount of
hydrogen gas. An absolu~e calibration curve was used for the
analysis. The resul~s are shown in Table 2.
WO 93/2124~ L'l 21 P(:~US93/02037
24
TABLE 2
Te~t Example No. 1 2 3 4 5
Cc~mp. Comp. ':
Soft material for Example 1 Example 2 ~xample 3 ~xample 1 Example 2
primary layer
Hard material for Example 4 Example 4 Example 4 Example 4 Example 4
0 ~econdary layer
Re~ult~ of Evaluation
1. Curing Rate
Gel Proportion (%~
at Dra~ing Rate
(m/min )
180 90 9~ 90 85 90
360 90 90 90 90 89
720 90 90 89 85 85
2. Environm~ntal Te~t
~Light Re~istance)
EXternal
Appear~nce No change No change No change No change Ch~nged
~eight Chantge ~ 0.5 -0.2 -0.3 -2.5 -0.3
Kydrogen Ga~
Generation ~l/gm)
Initi~l 0.2 0.2 0.2 0.2 8.0
After Te~t 5 6 4 300 20
The liquld curable resin composition of the present
invention exhibits a high curing rater its cured materials
has ~ low Young's modulus and a high gel ratio, provides
superior heat resistance and light resistance, and generates
35 Qnly a small amount of hydrogen gas. It is thus particularl~
suitable as a material for optical fiber coating. Oec~use of
its superior heat resistance, curability, and adherence f the
composition is not only applicable to an optical fiber
coating, but also useful as a protective coating material for
~arious types of substrates such as metals, plastics, wood,
WO93/21248 ~ 2 1 ~CTII~S93/02037
porcelain, glass, and the like, and as an optical molding
matérial, three~dimensional molding material~ printing plate
material, and the like.
